Low Density Polyolefin Resins With Low Molecular Weight and High Molecular Weight Components, and Films Made Therefrom

ABSTRACT

Disclosed herein are ethylene-based polymers produced using dual metallocene catalyst systems. These polymers have low densities, high molecular weights, and broad molecular weight distributions, as well as having the majority of the long chain branches in the lower molecular weight component of the polymer, and the majority of the short chain branches in the higher molecular weight component of the polymer. Films produced from these polymers have improved impact and puncture resistance.

BACKGROUND OF THE INVENTION

Polyolefins such as high density polyethylene (HDPE) homopolymer andlinear low density polyethylene (LLDPE) copolymer can be produced usingvarious combinations of catalyst systems and polymerization processes.Medium or high density polymers with a high molecular weight and a broadmolecular weight distribution often have a combination of relativelyeasy processing, superior melt strength, and a good balance of stiffnessand physical properties. In some end-use applications, however, it canbe beneficial to have this combination of properties, but also to haveimproved puncture, impact, and tear resistance. Accordingly, it is tothese ends that the present invention is directed.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

The present invention generally relates to new catalyst compositions,methods for preparing catalyst compositions, methods for using thecatalyst compositions to polymerize olefins, the polymer resins producedusing such catalyst compositions, and articles produced using thesepolymer resins. In particular, embodiments of the present invention aredirected to catalyst compositions employing two metallocene catalystcomponents. The first catalyst component generally can produce a lowermolecular component having high amounts of long chain branches (e.g., atwo carbon bridged metallocene compound containing two cyclopentadienylgroups, two indenyl groups, or a cyclopentadienyl and an indenyl group),while the second catalyst component generally can produce a highermolecular weight component having very few long chain branches (e.g., asingle atom bridged metallocene compound containing a fluorenyl group).Typically, the weight percentage of the first catalyst component can bein a range from about 25 to about 98%, based on the total weight of thefirst and second catalyst components. Such catalyst compositions can beused to produce, for example, ethylene-based copolymers having themajority of the long chain branches in the lower molecular weights, andthe majority of the short chain branches in the higher molecularweights.

The present invention also contemplates and encompasses olefinpolymerization processes. Such processes can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer under polymerization conditions to produce an olefin polymer.Generally, the catalyst composition employed can comprise any of thecatalyst component I metallocene compounds, any of the catalystcomponent II metallocene compounds, and any of the activators andoptional co-catalysts disclosed herein. For example, organoaluminumcompounds can be utilized in the catalyst compositions and/orpolymerization processes.

Polymers produced from the polymerization of olefins, resulting inhomopolymers, copolymers, terpolymers, etc., can be used to producevarious articles of manufacture. A representative and non-limitingexample of an olefin polymer (e.g., an ethylene copolymer) consistentwith embodiments of this invention can comprise a higher molecularweight component and a lower molecular weight component, and can becharacterized as having the following properties: a ratio of the Mp ofthe higher molecular weight component to the Mp of the lower molecularweight component in a range from about 5:1 to about 100:1, a number ofLCB of the lower molecular weight component in a range from about 5 toabout 50 LCB per million total carbon atoms, and a number of LCB of thehigher molecular weight component of less than or equal to about 5 LCBper million total carbon atoms. Another representative and non-limitingethylene-based polymer described herein can have a lower molecularweight component having a Mp in a range from about 15 to about 80kg/mol, and from about 5 to about 50 LCB per million total carbon atoms,and a higher molecular weight component having a Mp in a range fromabout 150 to about 800 kg/mol, and less than or equal to about 5 LCB permillion total carbon atoms. Yet another representative and non-limitingethylene-based polymer described herein can have a ratio of the Mp ofthe higher molecular weight component to the Mp of the lower molecularweight component in a range from about 5:1 to about 100:1, and a ratioof the number of LCB of the polymer to the number of LCB of the highermolecular weight component, per millions total carbon atoms, in a rangefrom about 2:1 to about 100:1. And yet another representative andnon-limiting ethylene-based polymer described herein can have a ratio ofthe Mp of the higher molecular weight component to the Mp of the lowermolecular weight component in a range from about 5:1 to about 100:1, anumber of LCB of the higher molecular weight component of less than orequal to about 5 LCB per million total carbon atoms, and a number of LCBof the olefin polymer in a range from about 2 to about 30 LCB permillion total carbon atoms. Moreover, blown films comprising olefinpolymers disclosed herein, for instance, having a melt index less thanor equal to about 0.4 g/10 min, can have very high puncture/impactresistance properties, such as a dart impact strength greater than orequal to about 300 g/mil.

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations may be provided inaddition to those set forth herein. For example, certain aspects andembodiments may be directed to various feature combinations andsub-combinations described in the detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 2.

FIG. 2 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 3.

FIG. 3 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 4.

FIG. 4 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 5.

FIG. 5 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 6.

FIG. 6 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 7.

FIG. 7 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 8.

FIG. 8 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 9.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997), can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

While compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methodscan also “consist essentially of” or “consist of” the various componentsor steps, unless stated otherwise. For example, a catalyst compositionconsistent with embodiments of the present invention can comprise;alternatively, can consist essentially of; or alternatively, can consistof; (i) catalyst component I, (ii) catalyst component II, (iii) anactivator, and (iv) optionally, a co-catalyst.

The terms “a,” “an,” “the,” etc., are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “an activator-support” or “a metallocenecompound” is meant to encompass one, or mixtures or combinations of morethan one, activator-support or metallocene compound, respectively,unless otherwise specified.

Generally, groups of elements are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements can be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.Unless otherwise specified, “substituted” is intended to be non-limitingand include inorganic substituents or organic substituents as understoodby one of ordinary skill in the art.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thepresence of one or more halogen atoms replacing an equivalent number ofhydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is usedherein in accordance with the definition specified by IUPAC: a univalentgroup formed by removing a hydrogen atom from a hydrocarbon (that is, agroup containing only carbon and hydrogen). Non-limiting examples ofhydrocarbyl groups include alkyl, alkenyl, aryl, and aralkyl groups,amongst other groups.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth. A copolymer isderived from an olefin monomer and one olefin comonomer, while aterpolymer is derived from an olefin monomer and two olefin comonomers.Accordingly, “polymer” encompasses copolymers, terpolymers, etc.,derived from any olefin monomer and comonomer(s) disclosed herein.Similarly, an ethylene polymer would include ethylene homopolymers,ethylene copolymers, ethylene terpolymers, and the like. As an example,an olefin copolymer, such as an ethylene copolymer, can be derived fromethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. Ifthe monomer and comonomer were ethylene and 1-hexene, respectively, theresulting polymer can be categorized an as ethylene/1-hexene copolymer.

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc. Therefore,a copolymerization process can involve contacting one olefin monomer(e.g., ethylene) and one olefin comonomer (e.g., 1-hexene) to produce acopolymer.

The term “co-catalyst” is used generally herein to refer to compoundssuch as aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, organoaluminum compounds, organozinccompounds, organomagnesium compounds, organolithium compounds, and thelike, that can constitute one component of a catalyst composition, whenused, for example, in addition to an activator-support. The term“co-catalyst” is used regardless of the actual function of the compoundor any chemical mechanism by which the compound may operate.

The terms “chemically-treated solid oxide,” “treated solid oxidecompound,” and the like, are used herein to indicate a solid, inorganicoxide of relatively high porosity, which can exhibit Lewis acidic orBrønsted acidic behavior, and which has been treated with anelectron-withdrawing component, typically an anion, and which iscalcined. The electron-withdrawing component is typically anelectron-withdrawing anion source compound. Thus, the chemically-treatedsolid oxide can comprise a calcined contact product of at least onesolid oxide with at least one electron-withdrawing anion sourcecompound. Typically, the chemically-treated solid oxide comprises atleast one acidic solid oxide compound. The “activator-support” of thepresent invention can be a chemically-treated solid oxide. The terms“support” and “activator-support” are not used to imply these componentsare inert, and such components should not be construed as an inertcomponent of the catalyst composition. The term “activator,” as usedherein, refers generally to a substance that is capable of converting ametallocene component into a catalyst that can polymerize olefins, orconverting a contact product of a metallocene component and a componentthat provides an activatable ligand (e.g., an alkyl, a hydride) to themetallocene, when the metallocene compound does not already comprisesuch a ligand, into a catalyst that can polymerize olefins. This term isused regardless of the actual activating mechanism. Illustrativeactivators include activator-supports, aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and the like.Aluminoxanes, organoboron or organoborate compounds, and ionizing ioniccompounds generally are referred to as activators if used in a catalystcomposition in which an activator-support is not present. If thecatalyst composition contains an activator-support, then thealuminoxane, organoboron or organoborate, and ionizing ionic materialsare typically referred to as co-catalysts.

The term “metallocene” as used herein describes compounds comprising atleast one η³ to η⁵-cycloalkadienyl-type moiety, wherein η³ toη⁵-cycloalkadienyl moieties include cyclopentadienyl ligands, indenylligands, fluorenyl ligands, and the like, including partially saturatedor substituted derivatives or analogs of any of these. Possiblesubstituents on these ligands may include H, therefore this inventioncomprises ligands such as tetrahydroindenyl, tetrahydrofluorenyl,octahydrofluorenyl, partially saturated indenyl, partially saturatedfluorenyl, substituted partially saturated indenyl, substitutedpartially saturated fluorenyl, and the like. In some contexts, themetallocene is referred to simply as the “catalyst,” in much the sameway the term “co-catalyst” is used herein to refer to, for example, anorganoaluminum compound.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of thedisclosed or claimed catalyst composition/mixture/system, the nature ofthe active catalytic site, or the fate of the co-catalyst, themetallocene compound(s), or the activator (e.g., activator-support),after combining these components. Therefore, the terms “catalystcomposition,” “catalyst mixture,” “catalyst system,” and the like,encompass the initial starting components of the composition, as well aswhatever product(s) may result from contacting these initial startingcomponents, and this is inclusive of both heterogeneous and homogenouscatalyst systems or compositions. The terms “catalyst composition,”“catalyst mixture,” “catalyst system,” and the like, can be usedinterchangeably throughout this disclosure.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of thecompositions described herein. Combining additional materials orcomponents can be done by any suitable method. Further, the term“contact product” includes mixtures, blends, solutions, slurries,reaction products, and the like, or combinations thereof. Although“contact product” can include reaction products, it is not required forthe respective components to react with one another. Similarly, the term“contacting” is used herein to refer to materials which can be blended,mixed, slurried, dissolved, reacted, treated, or otherwise contacted insome other manner.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

Applicants disclose several types of ranges in the present invention.When Applicants disclose or claim a range of any type, Applicants'intent is to disclose or claim individually each possible number thatsuch a range could reasonably encompass, including end points of therange as well as any sub-ranges and combinations of sub-rangesencompassed therein. For example, when the Applicants disclose or claima chemical moiety having a certain number of carbon atoms, Applicants'intent is to disclose or claim individually every possible number thatsuch a range could encompass, consistent with the disclosure herein. Forexample, the disclosure that a moiety is a C₁ to C₁₈ hydrocarbyl group,or in alternative language, a hydrocarbyl group having from 1 to 18carbon atoms, as used herein, refers to a moiety that can have 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, aswell as any range between these two numbers (for example, a C₁ to C₈hydrocarbyl group), and also including any combination of ranges betweenthese two numbers (for example, a C₂ to C₄ and a C₁₂ to C₁₆ hydrocarbylgroup).

Similarly, another representative example follows for the number-averagemolecular weight (Mn) of an olefin polymer produced in an embodiment ofthis invention. By a disclosure that the Mn can be in a range from about10 to about 50 kg/mol, Applicants intend to recite that the Mn can beany molecular weight in the range and, for example, can be equal toabout 10, about 15, about 20, about 25, about 30, about 35, about 40,about 45, or about 50 kg/mol. Additionally, the Mn can be within anyrange from about 10 to about 50 (for example, from about 10 to about25), and this also includes any combination of ranges between about 10and about 50 (for example, the Mn can be in a range from about 10 toabout 20, or from about 25 to about 45 kg/mol). Likewise, all otherranges disclosed herein should be interpreted in a manner similar tothese two examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to new catalystcompositions, methods for preparing catalyst compositions, methods forusing the catalyst compositions to polymerize olefins, the polymerresins produced using such catalyst compositions, and articles producedusing these polymer resins. In particular, the present invention relatesto catalyst compositions containing two metallocene components, topolymerization processes utilizing such catalyst compositions, and tothe resulting olefin polymers produced from the polymerizationprocesses.

Catalyst Component I

Catalyst component I generally can produce a lower molecular weightcomponent having more long chain branches and less short chain branchesthan the higher molecular weight component. Suitable catalyst componentI metallocene compounds generally can produce a lower molecular weightcomponent of the polymer such that the ratio of the number of LCB of thelower molecular weight component to the number of LCB of the highermolecular weight component, per millions total carbon atoms, typicallycan be in a range from about 4:1 to about 100:1, or from about 5:1 toabout 50:1, e.g., about 8:1, about 10:1, about 15:1, about 20:1, and soforth.

Catalyst component I can comprise a two carbon bridged metallocenecompound containing two cyclopentadienyl groups, two indenyl groups, ora cyclopentadienyl and an indenyl group. In one embodiment, forinstance, catalyst component I can comprise a two carbon bridged,zirconium based metallocene compound containing two cyclopentadienylgroups, two indenyl groups, or a cyclopentadienyl and an indenyl group.In another embodiment, catalyst component I can comprise a two carbonbridged, zirconium based metallocene compound containing two indenylgroups.

Catalyst component I can comprise, in particular embodiments of thisinvention, a two carbon bridged metallocene compound having formula (A):

Within formula (A), M¹, Cp¹, Cp², E¹, and each X are independentelements of the two carbon bridged metallocene compound. Accordingly,the metallocene compound having formula (A) can be described using anycombination of M¹, Cp¹, Cp², E¹, and X disclosed herein.

Unless otherwise specified, formula (A) above, any other structuralformulas disclosed herein, and any metallocene complex, compound, orspecies disclosed herein are not designed to show stereochemistry orisomeric positioning of the different moieties (e.g., these formulas arenot intended to display cis or trans isomers, or R or Sdiastereoisomers), although such compounds are contemplated andencompassed by these formulas and/or structures.

In accordance with embodiments of this invention, the metal in formula(A), M¹ can be Zr or Hf. In one embodiment, for instance, M¹ can be Zr,while in another embodiment, M¹ can be Hf.

Each X in formula (A) independently can be a monoanionic ligand. In someembodiments, suitable monoanionic ligands can include, but are notlimited to, H (hydride), BH₄, a halide, a C₁ to C₃₆ hydrocarbyl group, aC₁ to C₃₆ hydrocarboxy group, a C₁ to C₃₆ hydrocarbylaminyl group, a C₁to C₃₆ hydrocarbylsilyl group, a C₁ to C₃₆ hydrocarbylaminylsilyl group,—OBR¹ ₂, or —OSO₂R¹, wherein R¹ is a C₁ to C₃₆ hydrocarbyl group. It iscontemplated that each X can be either the same or a differentmonoanionic ligand.

In one embodiment, each X independently can be H, BH₄, a halide (e.g.,F, Cl, Br, etc.), a C₁ to C₁₈ hydrocarbyl group, a C₁ to C₁₈hydrocarboxy group, a C₁ to C₁₈ hydrocarbylaminyl group, a C₁ to C₁₈hydrocarbylsilyl group, or a C₁ to C₁₈ hydrocarbylaminylsilyl group.Alternatively, each X independently can be H, BH₄, a halide, OBR¹ ₂, orOSO₂R¹, wherein R¹ is a C₁ to C₁₈ hydrocarbyl group. In anotherembodiment, each X independently can be H, BH₄, a halide, a C₁ to C₁₂hydrocarbyl group, a C₁ to C₁₂ hydrocarboxy group, a C₁ to C₁₂hydrocarbylaminyl group, a C₁ to C₁₂ hydrocarbylsilyl group, a C₁ to C₁₂hydrocarbylaminylsilyl group, OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ toC₁₂ hydrocarbyl group. In another embodiment, each X independently canbe H, BH₄, a halide, a C₁ to C₁₀ hydrocarbyl group, a C₁ to C₁₀hydrocarboxy group, a C₁ to C₁₀ hydrocarbylaminyl group, a C₁ to C₁₀hydrocarbylsilyl group, a C₁ to C₁₀ hydrocarbylaminylsilyl group, OBR¹₂, or OSO₂R¹, wherein R¹ is a C₁ to C₁₀ hydrocarbyl group. In yetanother embodiment, each X independently can be H, BH₄, a halide, a C₁to C₈ hydrocarbyl group, a C₁ to C₈ hydrocarboxy group, a C₁ to C₈hydrocarbylaminyl group, a C₁ to C₈ hydrocarbylsilyl group, a C₁ to C₈hydrocarbylaminylsilyl group, OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ toC₈ hydrocarbyl group. In still another embodiment, each X independentlycan be a halide or a C₁ to C₁₈ hydrocarbyl group. For example, each Xcan be Cl.

The hydrocarbyl group which can be an X (one or both) in formula (A) canbe a C₁ to C₃₆ hydrocarbyl group, including, but not limited to, a C₁ toC₃₆ alkyl group, a C₂ to C₃₆ alkenyl group, a C₄ to C₃₆ cycloalkylgroup, a C₆ to C₃₆ aryl group, or a C₇ to C₃₆ aralkyl group. Forinstance, each X independently can be a C₁ to C₁₈ alkyl group, a C₂ toC₁₈ alkenyl group, a C₄ to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group,or a C₇ to C₁₈ aralkyl group; alternatively, each X independently can bea C₁ to C₁₂ alkyl group, a C₂ to C₁₂ alkenyl group, a C₄ to C₁₂cycloalkyl group, a C₆ to C₁₂ aryl group, or a C₇ to C₁₂ aralkyl group;alternatively, each X independently can be a C₁ to C₁₀ alkyl group, a C₂to C₁₀ alkenyl group, a C₄ to C₁₀ cycloalkyl group, a C₆ to C₁₀ arylgroup, or a C₇ to C₁₀ aralkyl group; or alternatively, each Xindependently can be a C₁ to C₅ alkyl group, a C₂ to C₅ alkenyl group, aC₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, or a C₇ to C₈ aralkylgroup.

Accordingly, in some embodiments, the alkyl group which can be an X informula (A) can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, a undecyl group, a dodecyl group, atridecyl group, a tetradecyl group, a pentadecyl group, a hexadecylgroup, a heptadecyl group, or an octadecyl group; or alternatively, amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, ora decyl group. In some embodiments, the alkyl group which can be an X informula (A) can be a methyl group, an ethyl group, a n-propyl group, aniso-propyl group, a n-butyl group, an iso-butyl group, a sec-butylgroup, a tert-butyl group, a n-pentyl group, an iso-pentyl group, asec-pentyl group, or a neopentyl group; alternatively, a methyl group,an ethyl group, an iso-propyl group, a tert-butyl group, or a neopentylgroup; alternatively, a methyl group; alternatively, an ethyl group;alternatively, a n-propyl group; alternatively, an iso-propyl group;alternatively, a tert-butyl group; or alternatively, a neopentyl group.

Suitable alkenyl groups which can be an X in formula (A) can include,but are not limited to, an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, a decenyl group, a undecenyl group, a dodecenylgroup, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, ahexadecenyl group, a heptadecenyl group, or an octadecenyl group. Suchalkenyl groups can be linear or branched, and the double bond can belocated anywhere in the chain. In one embodiment, each X in formula (A)independently can be an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, or a decenyl group, while in another embodiment,each X in formula (A) independently can be an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, or a hexenyl group. Forexample, an X can be an ethenyl group; alternatively, a propenyl group;alternatively, a butenyl group; alternatively, a pentenyl group; oralternatively, a hexenyl group. In yet another embodiment, an X can be aterminal alkenyl group, such as a C₃ to C₁₈ terminal alkenyl group, a C₃to C₁₂ terminal alkenyl group, or a C₃ to C₈ terminal alkenyl group.Illustrative terminal alkenyl groups can include, but are not limitedto, a prop-2-en-1-yl group, a bute-3-en-1-yl group, a pent-4-en-1-ylgroup, a hex-5-en-1-yl group, a hept-6-en-1-yl group, an octe-7-en-1-ylgroup, a non-8-en-1-yl group, a dece-9-en-1-yl group, and so forth.

Each X in formula (A) can be a cycloalkyl group, including, but notlimited to, a cyclobutyl group, a substituted cyclobutyl group, acyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group,a substituted cyclohexyl group, a cycloheptyl group, a substitutedcycloheptyl group, a cyclooctyl group, or a substituted cyclooctylgroup. For example, an X in formula (A) can be a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group. Moreover, each X in formula (A) independently can be acyclobutyl group or a substituted cyclobutyl group; alternatively, acyclopentyl group or a substituted cyclopentyl group; alternatively, acyclohexyl group or a substituted cyclohexyl group; alternatively, acycloheptyl group or a substituted cycloheptyl group; alternatively, acyclooctyl group or a substituted cyclooctyl group; alternatively, acyclopentyl group; alternatively, a substituted cyclopentyl group;alternatively, a cyclohexyl group; or alternatively, a substitutedcyclohexyl group. Substituents which can be utilized for the substitutedcycloalkyl group are independently disclosed herein and can be utilizedwithout limitation to further describe the substituted cycloalkyl groupwhich can be an X in formula (A).

In some embodiments, the aryl group which can be an X in formula (A) canbe a phenyl group, a substituted phenyl group, a naphthyl group, or asubstituted naphthyl group. In an embodiment, the aryl group can be aphenyl group or a substituted phenyl group; alternatively, a naphthylgroup or a substituted naphthyl group; alternatively, a phenyl group ora naphthyl group; alternatively, a substituted phenyl group or asubstituted naphthyl group; alternatively, a phenyl group; oralternatively, a naphthyl group. Substituents which can be utilized forthe substituted phenyl groups or substituted naphthyl groups areindependently disclosed herein and can be utilized without limitation tofurther describe the substituted phenyl groups or substituted naphthylgroups which can be an X in formula (A).

In an embodiment, the substituted phenyl group which can be an X informula (A) can be a 2-substituted phenyl group, a 3-substituted phenylgroup, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other embodiments, the substitutedphenyl group can be a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.Substituents which can be utilized for these specific substituted phenylgroups are independently disclosed herein and can be utilized withoutlimitation to further describe these substituted phenyl groups which canbe an X group(s) in formula (A).

In some embodiments, the aralkyl group which can be an X group informula (A) can be a benzyl group or a substituted benzyl group. In anembodiment, the aralkyl group can be a benzyl group or, alternatively, asubstituted benzyl group. Substituents which can be utilized for thesubstituted aralkyl group are independently disclosed herein and can beutilized without limitation to further describe the substituted aralkylgroup which can be an X group(s) in formula (A).

In an embodiment, each non-hydrogen substituent(s) for the substitutedcycloalkyl group, substituted aryl group, or substituted aralkyl groupwhich can be an X in formula (A) independently can be a C₁ to C₁₈hydrocarbyl group; alternatively, a C₁ to C₈ hydrocarbyl group; oralternatively, a C₁ to C₅ hydrocarbyl group. Specific hydrocarbyl groupsare independently disclosed herein and can be utilized withoutlimitation to further describe the substituents of the substitutedcycloalkyl groups, substituted aryl groups, or substituted aralkylgroups which can be an X in formula (A). For instance, the hydrocarbylsubstituent can be an alkyl group, such as a methyl group, an ethylgroup, a n-propyl group, an isopropyl group, a n-butyl group, asec-butyl group, an isobutyl group, a tert-butyl group, a n-pentylgroup, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, atert-pentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group,or a neo-pentyl group, and the like. Furthermore, the hydrocarbylsubstituent can be a benzyl group, a phenyl group, a tolyl group, or axylyl group, and the like.

A hydrocarboxy group is used generically herein to include, forinstance, alkoxy, aryloxy, aralkoxy, -(alkyl, aryl, oraralkyl)-O-(alkyl, aryl, or aralkyl) groups, and —O(CO)-(hydrogen orhydrocarbyl) groups, and these groups can comprise up to about 36 carbonatoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ to C₁₀, or C₁ to C₈ hydrocarboxygroups). Illustrative and non-limiting examples of hydrocarboxy groupswhich can be an X in formula (A) can include, but are not limited to, amethoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group,an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxygroup, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a2-methyl-1-butoxy group, a tert-pentoxy group, a 3-methyl-1-butoxygroup, a 3-methyl-2-butoxy group, a neo-pentoxy group, a phenoxy group,a toloxy group, a xyloxy group, a 2,4,6-trimethylphenoxy group, abenzoxy group, an acetylacetonate group (acac), a formate group, anacetate group, a stearate group, an oleate group, a benzoate group, andthe like. In an embodiment, the hydrocarboxy group which can be an X informula (A) can be a methoxy group; alternatively, an ethoxy group;alternatively, an n-propoxy group; alternatively, an isopropoxy group;alternatively, an n-butoxy group; alternatively, a sec-butoxy group;alternatively, an isobutoxy group; alternatively, a tert-butoxy group;alternatively, an n-pentoxy group; alternatively, a 2-pentoxy group;alternatively, a 3-pentoxy group; alternatively, a 2-methyl-1-butoxygroup; alternatively, a tert-pentoxy group; alternatively, a3-methyl-1-butoxy group, alternatively, a 3-methyl-2-butoxy group;alternatively, a neo-pentoxy group; alternatively, a phenoxy group;alternatively, a toloxy group; alternatively, a xyloxy group;alternatively, a 2,4,6-trimethylphenoxy group; alternatively, a benzoxygroup; alternatively, an acetylacetonate group; alternatively, a formategroup; alternatively, an acetate group; alternatively, a stearate group;alternatively, an oleate group; or alternatively, a benzoate group.

The term hydrocarbylaminyl group is used generically herein to refercollectively to, for instance, alkylaminyl, arylaminyl, aralkylaminyl,dialkylaminyl, diarylaminyl, diaralkylaminyl, and -(alkyl, aryl, oraralkyl)-N-(alkyl, aryl, or aralkyl) groups, and unless otherwisespecified, the hydrocarbylaminyl groups which can be an X in formula (A)can comprise up to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁to C₁₀, or C₁ to C₈ hydrocarbylaminyl groups). Accordingly,hydrocarbylaminyl is intended to cover both (mono)hydrocarbylaminyl anddihydrocarbylaminyl groups. In some embodiments, the hydrocarbylaminylgroup which can be an X in formula (A) can be, for instance, amethylaminyl group (—NHCH₃), an ethylaminyl group (—NHCH₂CH₃), ann-propylaminyl group (—NHCH₂CH₂CH₃), an iso-propylaminyl group(—NHCH(CH₃)₂), an n-butylaminyl group (—NHCH₂CH₂CH₂CH₃), a t-butylaminylgroup (—NHC(CH₃)₃), an n-pentylaminyl group (—NHCH₂CH₂CH₂CH₂CH₃), aneo-pentylaminyl group (—NHCH₂C(CH₃)₃), a phenylaminyl group (—NHC₆H₅),a tolylaminyl group (—NHC₆H₄CH₃), or a xylylaminyl group(—NHC₆H₃(CH₃)₂); alternatively, a methylaminyl group; alternatively, anethylaminyl group; alternatively, a propylaminyl group; oralternatively, a phenylaminyl group. In other embodiments, thehydrocarbylaminyl group which can be an X in formula (A) can be, forinstance, a dimethylaminyl group (—N(CH₃)₂), a diethylaminyl group(—N(CH₂CH₃)₂), a di-n-propylaminyl group (—N(CH₂CH₂CH₃)₂), adi-iso-propylaminyl group (—N(CH(CH₃)₂)₂), a di-n-butylaminyl group(—N(CH₂CH₂CH₂CH₃)₂), a di-t-butylaminyl group (—N(C(CH₃)₃)₂), adi-n-pentylaminyl group (—N(CH₂CH₂CH₂CH₂CH₃)₂), a di-neo-pentylaminylgroup (—N(CH₂C(CH₃)₃)₂), a di-phenylaminyl group (—N(C₆H₅)₂), adi-tolylaminyl group (—N(C₆H₄CH₃)₂), or a di-xylylaminyl group(—N(C₆H₃(CH₃)₂)₂); alternatively, a dimethylaminyl group; alternatively,a di-ethylaminyl group; alternatively, a di-n-propylaminyl group; oralternatively, a di-phenylaminyl group.

In accordance with some embodiments disclosed herein, each Xindependently can be a C₁ to C₃₆ hydrocarbylsilyl group; alternatively,a C₁ to C₂₄ hydrocarbylsilyl group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; or alternatively, a C₁ to C₈ hydrocarbylsilylgroup. In an embodiment, each hydrocarbyl (one or more) of thehydrocarbylsilyl group can be any hydrocarbyl group disclosed herein(e.g., a C₁ to C₅ alkyl group, a C₂ to C₅ alkenyl group, a C₅ to C₈cycloalkyl group, a C₆ to C₈ aryl group, a C₇ to C₈ aralkyl group,etc.). As used herein, hydrocarbylsilyl is intended to cover(mono)hydrocarbylsilyl (—SiH₂R), dihydrocarbylsilyl (—SiHR₂), andtrihydrocarbylsilyl (—SiR₃) groups, with R being a hydrocarbyl group. Inone embodiment, the hydrocarbylsilyl group can be a C₃ to C₃₆ or a C₃ toC₁₈ trihydrocarbylsilyl group, such as, for example, a trialkylsilylgroup or a triphenylsilyl group. Illustrative and non-limiting examplesof hydrocarbylsilyl groups which can be an X group(s) in formula (A) caninclude, but are not limited to, trimethylsilyl, triethylsilyl,tripropylsilyl (e.g., triisopropylsilyl), tributylsilyl, tripentylsilyl,triphenylsilyl, allyldimethylsilyl, and the like.

A hydrocarbylaminylsilyl group is used herein to refer to groupscontaining at least one hydrocarbon moiety, at least one N atom, and atleast one Si atom. Illustrative and non-limiting examples ofhydrocarbylaminylsilyl groups which can be an X can include, but are notlimited to —N(SiMe₃)₂, —N(SiEt₃)₂, and the like. Unless otherwisespecified, the hydrocarbylaminylsilyl groups which can be X can compriseup to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ to C₁₂, orC₁ to C₈ hydrocarbylaminylsilyl groups). In an embodiment, eachhydrocarbyl (one or more) of the hydrocarbylaminylsilyl group can be anyhydrocarbyl group disclosed herein (e.g., a C₁ to C₅ alkyl group, a C₂to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group,a C₇ to C₈ aralkyl group, etc.). Moreover, hydrocarbylaminylsilyl isintended to cover —NH(SiH₂R), —NH(SiHR₂), —NH(SiR₃), —N(SiH₂R)₂,—N(SiHR₂)₂, and —N(SiR₃)₂ groups, among others, with R being ahydrocarbyl group.

In an embodiment, each X independently can be —OBR¹ ₂ or —OSO₂R¹,wherein R¹ is a C₁ to C₃₆ hydrocarbyl group, or alternatively, a C₁ toC₁₈ hydrocarbyl group. The hydrocarbyl group in OBR¹ ₂ and/or OSO₂R¹independently can be any hydrocarbyl group disclosed herein, such as,for instance, a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenyl group, a C₄to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group, or a C₇ to C₁₈ aralkylgroup; alternatively, a C₁ to C₁₂ alkyl group, a C₂ to C₁₂ alkenylgroup, a C₄ to C₁₂ cycloalkyl group, a C₆ to C₁₂ aryl group, or a C₇ toC₁₂ aralkyl group; or alternatively, a C₁ to C₈ alkyl group, a C₂ to C₈alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, or aC₇ to C₈ aralkyl group.

In one embodiment, each X independently can be H, BH₄, a halide, or a C₁to C₃₆ hydrocarbyl group, hydrocarboxy group, hydrocarbylaminyl group,hydrocarbylsilyl group, or hydrocarbylaminylsilyl group, while inanother embodiment, each X independently can be H, BH₄, or a C₁ to C₁₈hydrocarboxy group, hydrocarbylaminyl group, hydrocarbylsilyl group, orhydrocarbylaminylsilyl group. In yet another embodiment, each Xindependently can be a halide; alternatively, a C₁ to C₁₈ hydrocarbylgroup; alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, aC₁ to C₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminylsilyl group. In still another embodiment, each X can beH; alternatively, F; alternatively, Cl; alternatively, Br;alternatively, I; alternatively, BH₄; alternatively, a C₁ to C₁₈hydrocarbyl group; alternatively, a C₁ to C₁₈ hydrocarboxy group;alternatively, a C₁ to C₁₈ hydrocarbylaminyl group; alternatively, a C₁to C₁₈ hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminylsilyl group.

Each X independently can be, in some embodiments, H, a halide, methyl,phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, formate,acetate, stearate, oleate, benzoate, an alkylaminyl, a dialkylaminyl, atrihydrocarbylsilyl, or a hydrocarbylaminylsilyl; alternatively, H, ahalide, methyl, phenyl, or benzyl; alternatively, an alkoxy, an aryloxy,or acetylacetonate; alternatively, an alkylaminyl or a dialkylaminyl;alternatively, a trihydrocarbylsilyl or hydrocarbylaminylsilyl;alternatively, H or a halide; alternatively, methyl, phenyl, benzyl, analkoxy, an aryloxy, acetylacetonate, an alkylaminyl, or a dialkylaminyl;alternatively, H; alternatively, a halide; alternatively, methyl;alternatively, phenyl; alternatively, benzyl; alternatively, an alkoxy;alternatively, an aryloxy; alternatively, acetylacetonate;alternatively, an alkylaminyl; alternatively, a dialkylaminyl;alternatively, a trihydrocarbylsilyl; or alternatively, ahydrocarbylaminylsilyl. In these and other embodiments, the alkoxy,aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, andhydrocarbylaminylsilyl can be a C₁ to C₃₆, a C₁ to C₁₈, a C₁ to C₁₂, ora C₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, and hydrocarbylaminylsilyl.

Moreover, each X independently can be, in certain embodiments, a halideor a C₁ to C₁₈ hydrocarbyl group; alternatively, a halide or a C₁ to C₈hydrocarbyl group; alternatively, F, Cl, Br, I, methyl, benzyl, orphenyl; alternatively, Cl, methyl, benzyl, or phenyl; alternatively, aC₁ to C₁₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; alternatively, aC₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; or alternatively,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, tolyl, benzyl, naphthyl, trimethylsilyl,triisopropylsilyl, triphenylsilyl, or allyldimethylsilyl.

In formula (A), Cp¹ and Cp² independently can be a cyclopentadienyl orindenyl group. In one embodiment, Cp¹ and Cp² contain no additionalsubstituents, e.g., other than the bridging group (discussed hereinbelow). For instance, Cp¹ and Cp² can be indenyl groups containing noadditional substituents, e.g., other than the bridging group.Alternatively, Cp¹ and Cp² independently can be a substituted indenyl orcyclopentadienyl group, for example, having 1 substituent, having 2substituents, having 3 substituents, having 4 substituents, having 5substituents, etc.

If present, each substituent on Cp¹ and Cp² independently can be H, ahalide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenatedhydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆hydrocarbylsilyl group. Importantly, each substituent on Cp¹ and/or Cp²can be either the same or a different substituent group. Moreover, eachsubstituent can be at any position on the respective cyclopentadienyl orindenyl ring structure that conforms with the rules of chemical valence.In an embodiment, the number of substituents on Cp¹ and/or on Cp² and/orthe positions of each substituent on Cp¹ and/or on Cp² are independentof each other. For instance, two or more substituents on Cp¹ can bedifferent, or alternatively, each substituent on Cp¹ can be the same.Additionally or alternatively, two or more substituents on Cp² can bedifferent, or alternatively, all substituents on Cp² can be the same. Inanother embodiment, one or more of the substituents on Cp¹ can bedifferent from the one or more of the substituents on Cp², oralternatively, all substituents on both Cp¹ and/or on Cp² can be thesame. In these and other embodiments, each substituent can be at anyposition on the respective cyclopentadienyl or indenyl ring structure.If substituted, Cp¹ and/or Cp² independently can have 1 substituent, 2substituents, 3 substituents, 4 substituents, and so forth.

In formula (A), each substituent on Cp¹ and/or on Cp² independently canbe H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenatedhydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆hydrocarbylsilyl group. In some embodiments, each substituentindependently can be H; alternatively, a halide; alternatively, a C₁ toC₁₈ hydrocarbyl group; alternatively, a C₁ to C₁₈ halogenatedhydrocarbyl group; alternatively, a C₁ to C₁₈ hydrocarboxy group;alternatively, a C₁ to C₁₈ hydrocarbylsilyl group; alternatively, a C₁to C₁₂ hydrocarbyl group or a C₁ to C₁₂ hydrocarbylsilyl group; oralternatively, a C₁ to C₈ alkyl group or a C₃ to C₈ alkenyl group. Thehalide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, andC₁ to C₃₆ hydrocarbylsilyl group which can be a substituent on Cp¹and/or on Cp² in formula (A) can be any halide, C₁ to C₃₆ hydrocarbylgroup, C₁ to C₃₆ hydrocarboxy group, and C₁ to C₃₆ hydrocarbylsilylgroup described herein (e.g., as pertaining to X in formula (A)). Asubstituent on Cp¹ and/or on Cp² in formula (A) can be, in certainembodiments, a C₁ to C₃₆ halogenated hydrocarbyl group, where thehalogenated hydrocarbyl group indicates the presence of one or morehalogen atoms replacing an equivalent number of hydrogen atoms in thehydrocarbyl group. The halogenated hydrocarbyl group often can be ahalogenated alkyl group, a halogenated alkenyl group, a halogenatedcycloalkyl group, a halogenated aryl group, or a halogenated aralkylgroup. Representative and non-limiting halogenated hydrocarbyl groupsinclude pentafluorophenyl, trifluoromethyl (CF₃), and the like.

As a non-limiting example, if present, each substituent on Cp¹ and/orCp¹ independently can be H, Cl, CF₃, a methyl group, an ethyl group, apropyl group, a butyl group (e.g., t-Bu), a pentyl group, a hexyl group,a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a tolyl group (or other substituted aryl group),a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, or anallyldimethylsilyl group; alternatively, H or a C₁ to C₁₈ hydrocarbylgroup; alternatively, H; alternatively, Cl; alternatively, CF₃;alternatively, a methyl group; alternatively, an ethyl group;alternatively, a propyl group; alternatively, a butyl group;alternatively, a pentyl group; alternatively, a hexyl group;alternatively, a heptyl group; alternatively, an octyl group, a nonylgroup; alternatively, a decyl group; alternatively, an ethenyl group;alternatively, a propenyl group; alternatively, a butenyl group;alternatively, a pentenyl group; alternatively, a hexenyl group;alternatively, a heptenyl group; alternatively, an octenyl group;alternatively, a nonenyl group; alternatively, a decenyl group;alternatively, a phenyl group; alternatively, a tolyl group;alternatively, a benzyl group; alternatively, a naphthyl group;alternatively, a trimethylsilyl group; alternatively, atriisopropylsilyl group; alternatively, a triphenylsilyl group; oralternatively, an allyldimethylsilyl group.

Bridging group E¹ in formula (A) can have the formula—CR^(1A)R^(1B)—CR^(2A)R^(2B)—, wherein R^(1A), R^(1B), R^(2A), andR^(2B) independently are H or a C₁-C₁₀ hydrocarbyl group (any C₁-C₁₀hydrocarbyl group disclosed herein). For instance, R^(1A), R^(1B),R^(2A), and R^(2B) independently can be H or a C₁ to C₈ hydrocarbylgroup; alternatively, H, a phenyl group, a C₁ to C₈ alkyl group, or a C₃to C₈ alkenyl group; alternatively, H, a methyl group, an ethyl group, apropyl group, a butyl group, a pentyl group, a hexyl group, a heptylgroup, an octyl group, a nonyl group, a decyl group, an ethenyl group, apropenyl group, a butenyl group, a pentenyl group, a hexenyl group, aheptenyl group, an octenyl group, a nonenyl group, a decenyl group, aphenyl group, a tolyl group, or a benzyl group; alternatively, H or amethyl group; or alternatively, H (i.e., E¹ is a bridging group of theformula —CH₂—CH₂—).

Illustrative and non-limiting examples of two-carbon bridged metallocenecompounds having formula (A) and/or suitable for use as catalystcomponent I can include compounds having the following formula:

wherein: M¹ can be Zr or Hf (e.g., M¹ can be Zr); E¹ can be a bridginggroup having the formula —CR^(1A)R^(1B)—CR^(2A)R^(2B)— (e.g., E¹ can be—CH₂—CH₂—); and each X independently can be a monoanionic ligand (e.g.,each X can be Cl).

In an embodiment, catalyst component I can comprise an unbridgedzirconium based metallocene compound with two cyclopentadienyl groups.In another embodiment, catalyst component I can comprise a single atombridged (C or Si), zirconium based metallocene compound with twocyclopentadienyl groups (e.g., with an alkyl substituent, such aspropyl). In yet another embodiment, catalyst component I can comprise asingle atom bridged (C or Si), zirconium based metallocene compound withtwo indenyl groups (e.g., meso-bridged). In still another embodiment,catalyst component I can comprise a 3-5 carbon atom bridged, zirconiumbased metallocene compound with two indenyl groups (e.g., rac-bridged).

Catalyst component I can comprise, in particular embodiments of thisinvention, an unbridged metallocene compound having formula (A2):

Within formula (A2), M¹, Cp^(A), Cp^(B), and each X are independentelements of the unbridged metallocene compound. Accordingly, theunbridged metallocene compound having formula (A2) can be describedusing any combination of M¹, Cp^(A), Cp^(B), and X disclosed herein. Themonoanionic ligand selections for X and transition metals for M¹ informula (A2) are the same as those described herein above for formula(A).

In formula (A2), Cp^(A) and Cp^(B) independently can be a substituted orunsubstituted cyclopentadienyl or indenyl group. In one embodiment,Cp^(A) and Cp^(B) independently can be an unsubstituted cyclopentadienylor indenyl group. Alternatively, Cp^(A) and Cp^(B) independently can bea substituted indenyl or cyclopentadienyl group, for example, having upto 5 substituents (e.g., any substituent disclosed herein). In aparticular embodiment, Cp^(A) and Cp^(B) independently can be anunsubstituted cyclopentadienyl group or an alkyl-substitutedcyclopentadienyl group, for example, with one methyl, ethyl, propyl, orbutyl substituent.

Illustrative and non-limiting examples of metallocene compounds havingformula (A2) and/or suitable for use as catalyst component I can includethe following compounds:

Catalyst Component II

Catalyst component II generally can produce a higher molecular weightcomponent having more short chain branches and less long chain branchesthan the lower molecular weight component. Catalyst component II cancomprise a single atom bridged metallocene compound containing afluorenyl group. In certain embodiments disclosed herein, for instance,catalyst component II can comprise a single atom bridged, zirconium orhafnium based metallocene compound containing a cyclopentadienyl groupand a fluorenyl group. Often, the single bridging atom can be a carbonatom or silicon atom. In some embodiments, the bridging group (bridgingatom and any substituents) can contain an aryl substituent (e.g., aphenyl group); additionally or alternatively, the bridging group cancontain an alkenyl substituent (e.g., a C₃-C₈ terminal alkenyl group).

Catalyst component II can comprise, in particular embodiments of thisinvention, a bridged metallocene compound having formula (B):

Within formula (B), M², Cp, E², R^(A), R^(B) , R^(X), R^(Y), and each Xare independent elements of the bridged metallocene compound.Accordingly, the bridged metallocene compound having formula (B) can bedescribed using any combination of M², Cp, E², R^(A), R^(B) , R^(X),R^(Y), and X disclosed herein.

The selections for M² and each X in formula (B) are the same as thosedescribed hereinabove for M¹ (Zr of Hf) and X (monoanionic ligand, e.g.,Cl) in formula (A). In formula (B), Cp can be a cyclopentadienyl group.In some embodiments, Cp can contain no additional substituents, e.g.,other than bridging group E², discussed herein below. In otherembodiments, Cp can be further substituted with 1 substituent, 2substituents, 3 substituents, and so forth. If present, each substituenton Cp independently can be H, a halide, a C₁ to C₃₆ hydrocarbyl group, aC₁ to C₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group,or a C₁ to C₃₆ hydrocarbylsilyl group. Importantly, each substituent onCp can be either the same or a different substituent group. Moreover,each substituent can be at any position on the cyclopentadienyl ringstructure that conforms with the rules of chemical valence. In general,any substituent on Cp, independently, can be H or any halide, C₁ to C₃₆hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl group described herein(e.g., as pertaining to substituents on Cp¹ and Cp¹ in formula (A)).

In one embodiment, for example, each substituent on Cp independently canbe H or a C₁ to C₁₈ hydrocarbyl group or C₁ to C₁₈ hydrocarbylsilylgroup. In another embodiment, each substituent on Cp independently canbe a C₁ to C₈ alkyl group or a C₃ to C₈ alkenyl group. In yet anotherembodiment, each substituent on Cp^(C) independently can be H, Cl, CF₃,a methyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, adecyl group, an ethenyl group, a propenyl group, a butenyl group, apentenyl group, a hexenyl group, a heptenyl group, an octenyl group, anonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzylgroup, a naphthyl group, a trimethylsilyl group, a triisopropylsilylgroup, a triphenylsilyl group, or an allyldimethylsilyl group.

Similarly, R^(X) and R^(Y) in formula (B) independently can be H or anyhalide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbylgroup, C₁ to C₃₆ hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl groupdisclosed herein (e.g., as pertaining to substituents on Cp¹ and Cp¹ informula (A)). In one embodiment, for example, R^(X) and R^(Y)independently can be H or a C₁ to C₁₂ hydrocarbyl group. In anotherembodiment, R^(X) and R^(Y) independently can be a C₁ to C₁₀ hydrocarbylgroup. In yet another embodiment, R^(X) and R^(Y) independently can beH, Cl, CF₃, a methyl group, an ethyl group, a propyl group, a butylgroup (e.g., t-Bu), a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, a hexenyl group, a heptenylgroup, an octenyl group, a nonenyl group, a decenyl group, a phenylgroup, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilylgroup, a triisopropylsilyl group, a triphenylsilyl group, or anallyldimethylsilyl group, and the like. In still another embodiment,R^(X) and R^(Y) independently can be a methyl group, an ethyl group, apropyl group, a butyl group, a pentyl group, a hexyl group, a heptylgroup, an octyl group, a nonyl group, a decyl group, an ethenyl group, apropenyl group, a butenyl group, a pentenyl group, a hexenyl group, aheptenyl group, an octenyl group, a nonenyl group, a decenyl group, aphenyl group, a tolyl group, or a benzyl group; or alternatively, H or aC₁ to C₆ linear or branched alkyl group (e.g., methyl, tert-butyl,etc.).

For the bridging group in formula (B), E² can be C or Si, and R^(A) andR^(B) independently can be H or any C₁ to C₁₈ hydrocarbyl groupdisclosed herein. R^(A) and R^(B) can be either the same or different.In some embodiments of this invention, E² can be C. In these and otherembodiments, R^(A) and R^(B) independently can be a C₁ to C₁₂hydrocarbyl group; alternatively, R^(A) and R^(B) independently can be aC₁ to C₈ hydrocarbyl group; alternatively, R^(A) and R^(B) independentlycan be a phenyl group, a C₁ to C₈ alkyl group, or a C₃ to C₈ alkenylgroup; alternatively, R^(A) and R^(B) independently can be a methylgroup, an ethyl group, a propyl group, a butyl group, a pentyl group, ahexyl group, a heptyl group, an octyl group, a nonyl group, a decylgroup, an ethenyl group, a propenyl group, a butenyl group, a pentenylgroup, a hexenyl group, a heptenyl group, an octenyl group, a nonenylgroup, a decenyl group, a phenyl group, a cyclohexylphenyl group, anaphthyl group, a tolyl group, or a benzyl group; or alternatively,R^(A) and R^(B) independently can be a methyl group, an ethyl group, apropyl group, a butyl group, a pentyl group, a hexyl group, a propenylgroup, a butenyl group, a pentenyl group, a hexenyl group, a phenylgroup, or a benzyl group. In particular embodiments of this invention,at least one of R^(A) and R^(B) can be a phenyl group; additionally oralternatively, at least one of R^(A) and R^(B) can be a C₃ to C₈terminal alkenyl group.

Illustrative and non-limiting examples of bridged metallocene compoundshaving formula (B) and/or suitable for use as catalyst component II caninclude the following compounds (Me=methyl, Ph=phenyl; t-Bu=tert-butyl):

and the like, as well as combinations thereof.

Catalyst component II is not limited solely to the bridged metallocenecompounds such as described above. Other suitable single atom bridgedmetallocene compounds are disclosed in U.S. Pat. Nos. 7,026,494,7,041,617, 7,226,886, 7,312,283, 7,517,939, and 7,619,047, which areincorporated herein by reference in their entirety.

Activator-Supports

The present invention encompasses various catalyst compositionscontaining an activator-support. In one embodiment, theactivator-support can comprise a solid oxide treated with anelectron-withdrawing anion. Alternatively, in another embodiment, theactivator-support can comprise a solid oxide treated with anelectron-withdrawing anion, the solid oxide containing a Lewis-acidicmetal ion. Non-limiting examples of suitable activator-supports aredisclosed in, for instance, U.S. Pat. Nos. 7,294,599, 7,601,665,7,884,163, and 8,309,485, which are incorporated herein by reference intheir entirety.

The solid oxide can encompass oxide materials such as alumina, “mixedoxides” thereof such as silica-alumina, coatings of one oxide onanother, and combinations and mixtures thereof. The mixed oxides such assilica-alumina can be single or multiple chemical phases with more thanone metal combined with oxygen to form the solid oxide. Examples ofmixed oxides that can be used to form an activator-support, eithersingly or in combination, can include, but are not limited to,silica-alumina, silica-titania, silica-zirconia, alumina-titania,alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria,aluminophosphate-silica, titania-zirconia, and the like. The solid oxideused herein also can encompass oxide materials such as silica-coatedalumina, as described in U.S. Pat. No. 7,884,163.

Accordingly, in one embodiment, the solid oxide can comprise silica,alumina, silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, silica-titania,zirconia, silica-zirconia, magnesia, boria, zinc oxide, any mixed oxidethereof, or any combination thereof. In another embodiment, the solidoxide can comprise alumina, silica-alumina, silica-coated alumina,aluminum phosphate, aluminophosphate, heteropolytungstate, titania,silica-titania, zirconia, silica-zirconia, magnesia, boria, or zincoxide, as well as any mixed oxide thereof, or any mixture thereof. Inanother embodiment, the solid oxide can comprise silica, alumina,titania, zirconia, magnesia, boria, zinc oxide, any mixed oxide thereof,or any combination thereof. In yet another embodiment, the solid oxidecan comprise silica-alumina, silica-coated alumina, silica-titania,silica-zirconia, alumina-boria, or any combination thereof. In stillanother embodiment, the solid oxide can comprise alumina,silica-alumina, silica-coated alumina, or any mixture thereof;alternatively, alumina; alternatively, silica-alumina; or alternatively,silica-coated alumina.

The silica-alumina or silica-coated alumina solid oxide materials whichcan be used can have an silica content from about 5 to about 95% byweight. In one embodiment, the silica content of these solid oxides canbe from about 10 to about 80%, or from about 20% to about 70%, silica byweight. In another embodiment, such materials can have silica contentsranging from about 15% to about 60%, or from about 25% to about 50%,silica by weight. The solid oxides contemplated herein can have anysuitable surface area, pore volume, and particle size, as would berecognized by those of skill in the art.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to oneembodiment, the electron-withdrawing component can be anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Examples of electron-withdrawing anions caninclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, tungstate, molybdate, and the like,including mixtures and combinations thereof. In addition, other ionic ornon-ionic compounds that serve as sources for these electron-withdrawinganions also can be employed. It is contemplated that theelectron-withdrawing anion can be, or can comprise, fluoride, chloride,bromide, phosphate, triflate, bisulfate, or sulfate, and the like, orany combination thereof, in some embodiments provided herein. In otherembodiments, the electron-withdrawing anion can comprise sulfate,bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate,fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate,fluorozirconate, fluorotitanate, and the like, or combinations thereof.Yet, in other embodiments, the electron-withdrawing anion can comprisefluoride and/or sulfate.

The activator-support generally can contain from about 1 to about 25 wt.% of the electron-withdrawing anion, based on the weight of theactivator-support. In particular embodiments provided herein, theactivator-support can contain from about 1 to about 20 wt. %, from about2 to about 20 wt. %, from about 3 to about 20 wt. %, from about 2 toabout 15 wt. %, from about 3 to about 15 wt. %, from about 3 to about 12wt. %, or from about 4 to about 10 wt. %, of the electron-withdrawinganion, based on the total weight of the activator-support.

In an embodiment, the activator-support can comprise fluorided alumina,chlorided alumina, bromided alumina, sulfated alumina, fluoridedsilica-alumina, chlorided silica-alumina, bromided silica-alumina,sulfated silica-alumina, fluorided silica-zirconia, chloridedsilica-zirconia, bromided silica-zirconia, sulfated silica-zirconia,fluorided silica-titania, fluorided silica-coated alumina, sulfatedsilica-coated alumina, phosphated silica-coated alumina, and the like,as well as any mixture or combination thereof. In another embodiment,the activator-support employed in the catalyst systems described hereincan be, or can comprise, a fluorided solid oxide and/or a sulfated solidoxide, non-limiting examples of which can include fluorided alumina,sulfated alumina, fluorided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, fluorided silica-coated alumina, sulfatedsilica-coated alumina, and the like, as well as combinations thereof. Inyet another embodiment, the activator-support can comprise fluoridedalumina; alternatively, chlorided alumina; alternatively, sulfatedalumina; alternatively, fluorided silica-alumina; alternatively,sulfated silica-alumina; alternatively, fluorided silica-zirconia;alternatively, chlorided silica-zirconia; alternatively, sulfatedsilica-coated alumina; or alternatively, fluorided silica-coatedalumina.

Various processes can be used to form activator-supports useful in thepresent invention. Methods of contacting the solid oxide with theelectron-withdrawing component, suitable electron withdrawing componentsand addition amounts, impregnation with metals or metal ions (e.g.,zinc, nickel, vanadium, titanium, silver, copper, gallium, tin,tungsten, molybdenum, zirconium, and the like, or combinations thereof),and various calcining procedures and conditions are disclosed in, forexample, U.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271,6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666,6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894,6,667,274, 6,750,302, 7,294,599, 7,601,665, 7,884,163, and 8,309,485,which are incorporated herein by reference in their entirety. Othersuitable processes and procedures for preparing activator-supports(e.g., fluorided solid oxides, sulfated solid oxides, etc.) are wellknown to those of skill in the art.

Co-Catalysts

In certain embodiments directed to catalyst compositions containing aco-catalyst, the co-catalyst can comprise a metal hydrocarbyl compound,examples of which include non-halide metal hydrocarbyl compounds, metalhydrocarbyl halide compounds, non-halide metal alkyl compounds, metalalkyl halide compounds, and so forth. The hydrocarbyl group (or alkylgroup) can be any hydrocarbyl (or alkyl) group disclosed herein.Moreover, in some embodiments, the metal of the metal hydrocarbyl can bea group 1, 2, 11, 12, 13, or 14 metal; alternatively, a group 13 or 14metal; or alternatively, a group 13 metal. Hence, in some embodiments,the metal of the metal hydrocarbyl (non-halide metal hydrocarbyl ormetal hydrocarbyl halide) can be lithium, sodium, potassium, rubidium,cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium,boron, aluminum, or tin; alternatively, lithium, sodium, potassium,magnesium, calcium, zinc, boron, aluminum, or tin; alternatively,lithium, sodium, or potassium; alternatively, magnesium or calcium;alternatively, lithium; alternatively, sodium; alternatively, potassium;alternatively, magnesium; alternatively, calcium; alternatively, zinc;alternatively, boron; alternatively, aluminum; or alternatively, tin. Insome embodiments, the metal hydrocarbyl or metal alkyl, with or withouta halide, can comprise a lithium hydrocarbyl or alkyl, a magnesiumhydrocarbyl or alkyl, a boron hydrocarbyl or alkyl, a zinc hydrocarbylor alkyl, or an aluminum hydrocarbyl or alkyl.

In particular embodiments directed to catalyst compositions containing aco-catalyst (e.g., the activator can comprise a solid oxide treated withan electron-withdrawing anion), the co-catalyst can comprise analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, an organoaluminum compound, an organozinccompound, an organomagnesium compound, or an organolithium compound, andthis includes any combinations of these materials. In one embodiment,the co-catalyst can comprise an organoaluminum compound. In anotherembodiment, the co-catalyst can comprise an aluminoxane compound, anorganoboron or organoborate compound, an ionizing ionic compound, anorganozinc compound, an organomagnesium compound, an organolithiumcompound, or any combination thereof. In yet another embodiment, theco-catalyst can comprise an aluminoxane compound; alternatively, anorganoboron or organoborate compound; alternatively, an ionizing ioniccompound; alternatively, an organozinc compound; alternatively, anorganomagnesium compound; or alternatively, an organolithium compound.

Specific non-limiting examples of suitable organoaluminum compounds caninclude trimethylaluminum (TMA), triethylaluminum (TEA),tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof. Representative andnon-limiting examples of aluminoxanes include methylaluminoxane,modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane,neopentylaluminoxane, and the like, or any combination thereof.Representative and non-limiting examples of organoboron/organoboratecompounds include N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron,and the like, or mixtures thereof.

Examples of ionizing ionic compounds can include, but are not limitedto, the following compounds: tri(n-butyl)ammoniumtetrakis(p-tolyl)borate, tri(n-butyl) ammonium tetrakis(m-tolyl)borate,tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)b orate,tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylaniliniumtetrakis(m-tolyl)borate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate,triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate,triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate,triphenylcarbenium tetrakis [3,5-bis(trifluoromethyl)phenyl]borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropyliumtetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetraphenylborate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, and thelike, or combinations thereof.

Exemplary organozinc compounds which can be used as co-catalysts caninclude, but are not limited to, dimethylzinc, diethylzinc,dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc,di(triethylsilyl)zinc, di(triisoproplysilyl)zinc,di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc,di(trimethylsilylmethyl)zinc, and the like, or combinations thereof.

Similarly, exemplary organomagnesium compounds can include, but are notlimited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium,dibutylmagnesium, dineopentylmagnesium,di(trimethylsilylmethyl)magnesium, methylmagnesium chloride,ethylmagnesium chloride, propylmagnesium chloride, butylmagnesiumchloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesiumchloride, methylmagnesium bromide, ethylmagnesium bromide,propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesiumbromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide,ethylmagnesium iodide, propylmagnesium iodide, butylmagnesium iodide,neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide,methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesiumethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide,trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide,ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesiumpropoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesiumpropoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide,propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesiumphenoxide, trimethylsilylmethylmagnesium phenoxide, and the like, or anycombinations thereof.

Likewise, exemplary organolithium compounds can include, but are notlimited to, methyllithium, ethyllithium, propyllithium, butyllithium(e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium,phenyllithium, tolyllithium, xylyllithium, benzyllithium,(dimethylphenyl)methyllithium, allyllithium, and the like, orcombinations thereof.

Co-catalysts that can be used in the catalyst compositions of thisinvention are not limited to the co-catalysts described above. Othersuitable co-catalysts are well known to those of skill in the artincluding, for example, those disclosed in U.S. Pat. Nos. 3,242,099,4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983, 7,294,5997,601,665, 7,884,163, 8,114,946, and 8,309,485, which are incorporatedherein by reference in their entirety.

Olefin Monomers

Unsaturated reactants that can be employed with catalyst compositionsand polymerization processes of this invention typically can includeolefin compounds having from 2 to 30 carbon atoms per molecule andhaving at least one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization, terpolymerization, etc.,reactions using an olefin monomer with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally can contain a major amount of ethylene (>50 molepercent) and a minor amount of comonomer (<50 mole percent), though thisis not a requirement. Comonomers that can be copolymerized with ethyleneoften can have from 3 to 20 carbon atoms, or from 3 to 10 carbon atoms,in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention can include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes (e.g., 1-octene), the four normal nonenes, thefive normal decenes, and the like, or mixtures of two or more of thesecompounds. Cyclic and bicyclic olefins, including but not limited to,cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like,also can be polymerized as described herein. Styrene can also beemployed as a monomer in the present invention. In an embodiment, theolefin monomer can comprise a C₂-C₂₀ olefin; alternatively, a C₂-C₂₀alpha-olefin; alternatively, a C₂-C₁₀ olefin; alternatively, a C₂-C₁₀alpha-olefin; alternatively, the olefin monomer can comprise ethylene;or alternatively, the olefin monomer can comprise propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer and the olefin comonomer independently can comprise, forexample, a C₂-C₂₀ alpha-olefin. In some embodiments, the olefin monomercan comprise ethylene or propylene, which is copolymerized with at leastone comonomer (e.g., a C₂-C₂₀ alpha-olefin, a C₃-C₂₀ alpha-olefin,etc.). According to one embodiment of this invention, the olefin monomerused in the polymerization process can comprise ethylene. In thisembodiment, examples of suitable olefin comonomers can include, but arenot limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene,isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene,2-heptene, 3-heptene, 1-octene, 1-decene, styrene, and the like, orcombinations thereof. According to another embodiment of the presentinvention, the olefin monomer can comprise ethylene, and the comonomercan comprise a C₃-C₁₀ alpha-olefin; alternatively, the comonomer cancomprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, orany combination thereof; alternatively, the comonomer can comprise1-butene, 1-hexene, 1-octene, or any combination thereof; alternatively,the comonomer can comprise 1-butene; alternatively, the comonomer cancomprise 1-hexene; or alternatively, the comonomer can comprise1-octene.

Generally, the amount of comonomer introduced into a polymerizationreactor system to produce a copolymer can be from about 0.01 to about 50weight percent of the comonomer based on the total weight of the monomerand comonomer. According to another embodiment of the present invention,the amount of comonomer introduced into a polymerization reactor systemcan be from about 0.01 to about 40 weight percent comonomer based on thetotal weight of the monomer and comonomer. In still another embodiment,the amount of comonomer introduced into a polymerization reactor systemcan be from about 0.1 to about 35 weight percent comonomer based on thetotal weight of the monomer and comonomer. Yet, in another embodiment,the amount of comonomer introduced into a polymerization reactor systemcan be from about 0.5 to about 20 weight percent comonomer based on thetotal weight of the monomer and comonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight.

According to one embodiment of the present invention, at least onemonomer/reactant can be ethylene (or propylene), so the polymerizationreaction can be a homopolymerization involving only ethylene (orpropylene), or a copolymerization with a different acyclic, cyclic,terminal, internal, linear, branched, substituted, or unsubstitutedolefin. In addition, the catalyst compositions of this invention can beused in the polymerization of diolefin compounds including, but notlimited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Catalyst Compositions

In some embodiments, the present invention can employ catalystcompositions containing catalyst component I, catalyst component II, anactivator (one or more than one), and optionally, a co-catalyst. Thesecatalyst compositions can be utilized to producepolyolefins—homopolymers, copolymers, and the like—for a variety ofend-use applications. Catalyst components I and II are discussedhereinabove. In embodiments of the present invention, it is contemplatedthat the catalyst composition can contain more than one catalystcomponent I metallocene compound, and/or more than one catalystcomponent II metallocene compound. Further, additional catalyticcompounds—other than those specified as catalyst component I or II—canbe employed in the catalyst compositions and/or the polymerizationprocesses, provided that the additional catalytic compound(s) does notdetract from the advantages disclosed herein. Additionally, more thanone activator also may be utilized.

The metallocene compounds of catalyst component I are discussedhereinabove. For instance, in some embodiments, catalyst component I cancomprise (or consist essentially of, or consist of) a two carbon bridgedmetallocene compound containing two cyclopentadienyl groups, two indenylgroups, or a cyclopentadienyl and an indenyl group (e.g., a metallocenecompound having formula (A)). The metallocene compounds of catalystcomponent II also are discussed hereinabove. For instance, in someembodiments, catalyst component II can comprise (or consist essentiallyof, or consist of) a single atom bridged metallocene compound containinga fluorenyl group (e.g., a metallocene compound having formula (B)).

Generally, catalyst compositions of the present invention can comprisecatalyst component I, catalyst component II, and an activator. Inembodiments of the invention, the activator can comprise anactivator-support (e.g., an activator-support comprising a solid oxidetreated with an electron-withdrawing anion). Activator-supports usefulin the present invention are disclosed hereinabove. Optionally, suchcatalyst compositions can further comprise one or more than oneco-catalyst compound or compounds (suitable co-catalysts, such asorganoaluminum compounds, also are discussed hereinabove). Thus, acatalyst composition of this invention can comprise catalyst componentI, catalyst component II, an activator-support, and an organoaluminumcompound. For instance, the activator-support can comprise (or consistessentially of, or consist of) fluorided alumina, chlorided alumina,bromided alumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, and the like, or combinations thereof;alternatively, the activator-support can comprise (or consistessentially of, or consist of) a fluorided solid oxide and/or a sulfatedsolid oxide. Additionally, the organoaluminum compound can comprise (orconsist essentially of, or consist of) trimethylaluminum,triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof. Accordingly, a catalystcomposition consistent with embodiments of the invention can comprise(or consist essentially of, or consist of) a two carbon bridged,zirconium based metallocene compound; a single atom bridged, zirconiumor hafnium based metallocene compound with cyclopentadienyl group and afluorenyl group; sulfated alumina (or fluorided silica-alumina, orfluorided silica-coated alumina); and triethylaluminum (ortriisobutylaluminum).

In another embodiment of the present invention, a catalyst compositionis provided which comprises catalyst component I, catalyst component II,an activator-support, and an organoaluminum compound, wherein thiscatalyst composition is substantially free of aluminoxanes, organoboronor organoborate compounds, ionizing ionic compounds, and/or othersimilar materials; alternatively, substantially free of aluminoxanes;alternatively, substantially free or organoboron or organoboratecompounds; or alternatively, substantially free of ionizing ioniccompounds. In these embodiments, the catalyst composition has catalystactivity, discussed below, in the absence of these additional materials.For example, a catalyst composition of the present invention can consistessentially of catalyst component I, catalyst component II, anactivator-support, and an organoaluminum compound, wherein no othermaterials are present in the catalyst composition which wouldincrease/decrease the activity of the catalyst composition by more thanabout 10% from the catalyst activity of the catalyst composition in theabsence of said materials.

However, in other embodiments of this invention, theseactivators/co-catalysts can be employed. For example, a catalystcomposition comprising catalyst component I, catalyst component II, andan activator-support can further comprise a co-catalyst. Suitableco-catalysts in this embodiment can include, but are not limited to,aluminoxane compounds, organoboron or organoborate compounds, ionizingionic compounds, organoaluminum compounds, organozinc compounds,organomagnesium compounds, organolithium compounds, and the like, or anycombination thereof; or alternatively, organoaluminum compounds,organozinc compounds, organomagnesium compounds, organolithiumcompounds, or any combination thereof. More than one co-catalyst can bepresent in the catalyst composition.

In a different embodiment, a catalyst composition is provided which doesnot require an activator-support. Such a catalyst composition cancomprise catalyst component I, catalyst component II, and an activator,wherein the activator comprises an aluminoxane compound, an organoboronor organoborate compound, an ionizing ionic compound, or combinationsthereof; alternatively, an aluminoxane compound; alternatively, anorganoboron or organoborate compound; or alternatively, an ionizingionic compound.

In a particular embodiment contemplated herein, the catalyst compositionis a catalyst composition comprising an activator (one or more thanone), only one catalyst component I metallocene compound, and only onecatalyst component II metallocene compound. In these and otherembodiments, the catalyst composition can comprise an activator (e.g.,an activator-support comprising a solid oxide treated with anelectron-withdrawing anion); only one two carbon bridged metallocenecompound containing two cyclopentadienyl groups, two indenyl groups, ora cyclopentadienyl and an indenyl group; only one single atom bridgedmetallocene compound containing a fluorenyl group; and optionally, aco-catalyst.

This invention further encompasses methods of making these catalystcompositions, such as, for example, contacting the respective catalystcomponents in any order or sequence.

According to an embodiment of this invention, the weight percentage ofcatalyst component I, based on the total weight of catalyst component Iand catalyst component II in the catalyst composition, typically canfall within a range from about 25 to about 98%, from about 40 to about95%, from about 55 to about 98%, or from about 60 to about 95%.

Generally, the weight ratio of organoaluminum compound toactivator-support can be in a range from about 10:1 to about 1:1000. Ifmore than one organoaluminum compound and/or more than oneactivator-support is employed, this ratio is based on the total weightof each respective component. In another embodiment, the weight ratio ofthe organoaluminum compound to the activator-support can be in a rangefrom about 3:1 to about 1:100, or from about 1:1 to about 1:50.

In some embodiments of this invention, the weight ratio of metallocenecompounds (total of catalyst component I and II) to activator-supportcan be in a range from about 1:1 to about 1:1,000,000. If more than oneactivator-support is employed, this ratio is based on the total weightof the activator-support. In another embodiment, this weight ratio canbe in a range from about 1:5 to about 1:100,000, or from about 1:10 toabout 1:10,000. Yet, in another embodiment, the weight ratio of themetallocene compounds to the activator-support can be in a range fromabout 1:20 to about 1:1000.

Catalyst compositions of the present invention generally have a catalystactivity greater than about 100 grams of polyethylene (homopolymer,copolymer, etc., as the context requires) per gram of activator-supportper hour (abbreviated g/g/hr). In another embodiment, the catalystactivity can greater than about 150, greater than about 250, or greaterthan about 500 g/g/hr. In still another embodiment, catalystcompositions of this invention can be characterized by having a catalystactivity greater than about 550, greater than about 650, or greater thanabout 750 g/g/hr. Yet, in another embodiment, the catalyst activity canbe greater than about 1000 g/g/hr. These activities are measured underslurry polymerization conditions, with a triisobutylaluminumco-catalyst, using isobutane as the diluent, at a polymerizationtemperature of about 90° C. and a reactor pressure of about 390 psig.Additionally, in some embodiments, the activator-support can comprisesulfated alumina, fluorided silica-alumina, or fluorided silica-coatedalumina, although not limited thereto.

Polymerization Processes

Catalyst compositions of the present invention can be used to polymerizeolefins to form homopolymers, copolymers, terpolymers, and the like. Onesuch process for polymerizing olefins in the presence of a catalystcomposition of the present invention can comprise contacting thecatalyst composition with an olefin monomer and optionally an olefincomonomer (one or more) in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition can comprise catalyst component I, catalystcomponent II, an activator, and an optional co-catalyst. Catalystcomponents I and II are discussed herein. For instance, catalystcomponent I can comprise a bridged metallocene compound having formula(A), and catalyst component II can comprise a bridged metallocenecompound having formula (B).

In accordance with one embodiment of the invention, the polymerizationprocess can employ a catalyst composition comprising catalyst componentI, catalyst component II, and an activator, wherein the activatorcomprises an activator-support. Activator-supports useful in thepolymerization processes of the present invention are disclosed herein.The catalyst composition, optionally, can further comprise one or morethan one organoaluminum compound or compounds (or other suitableco-catalyst). Thus, a process for polymerizing olefins in the presenceof a catalyst composition can employ a catalyst composition comprisingcatalyst component I, catalyst component II, an activator-support, andan organoaluminum compound. In some embodiments, the activator-supportcan comprise (or consist essentially of, or consist of) fluoridedalumina, chlorided alumina, bromided alumina, sulfated alumina,fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, and the like, or combinations thereof; or alternatively afluorided solid oxide and/or a sulfated solid oxide. In someembodiments, the organoaluminum compound can comprise (or consistessentially of, or consist of) trimethylaluminum, triethylaluminum,tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride,diethylaluminum ethoxide, diethylaluminum chloride, and the like, orcombinations thereof.

In accordance with another embodiment of the invention, thepolymerization process can employ a catalyst composition comprisingcatalyst component I, catalyst component II, an activator-support, andan optional co-catalyst, wherein the co-catalyst can comprise analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, an organoaluminum compound, an organozinccompound, an organomagnesium compound, or an organolithium compound, orany combination thereof. Hence, embodiments of this invention aredirected to a process for polymerizing olefins in the presence of acatalyst composition, the processes comprising contacting a catalystcomposition with an olefin monomer and optionally an olefin comonomer(one or more) in a polymerization reactor system under polymerizationconditions to produce an olefin polymer, and the catalyst compositioncan comprise catalyst component I, catalyst component II, anactivator-support, and an aluminoxane compound; alternatively, catalystcomponent I, catalyst component II, an activator-support, and anorganoboron or organoborate compound; alternatively, catalyst componentI, catalyst component II, an activator-support, and an ionizing ioniccompound; alternatively, catalyst component I, catalyst component II, anactivator-support, and an organoaluminum compound; alternatively,catalyst component I, catalyst component II, an activator-support, andan organozinc compound; alternatively, catalyst component I, catalystcomponent II, an activator-support, and an organomagnesium compound; oralternatively, catalyst component I, catalyst component II, anactivator-support, and an organolithium compound. Furthermore, more thanone co-catalyst can be employed, e.g., an organoaluminum compound and analuminoxane compound, an organoaluminum compound and an ionizing ioniccompound, etc.

In accordance with another embodiment of the invention, thepolymerization process can employ a catalyst composition comprising onlyone catalyst component I metallocene compound, only one catalystcomponent II metallocene compound, an activator-support, and anorganoaluminum compound.

In accordance with yet another embodiment of the invention, thepolymerization process can employ a catalyst composition comprisingcatalyst component I, catalyst component II, and an activator, whereinthe activator comprises an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, or combinationsthereof.

The catalyst compositions of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactor systems and reactors. The polymerization reactor system caninclude any polymerization reactor capable of polymerizing olefinmonomers and comonomers (one or more than one comonomer) to producehomopolymers, copolymers, terpolymers, and the like. The various typesof reactors include those that can be referred to as a batch reactor,slurry reactor, gas-phase reactor, solution reactor, high pressurereactor, tubular reactor, autoclave reactor, and the like, orcombinations thereof. Suitable polymerization conditions are used forthe various reactor types. Gas phase reactors can comprise fluidized bedreactors or staged horizontal reactors. Slurry reactors can comprisevertical or horizontal loops. High pressure reactors can compriseautoclave or tubular reactors. Reactor types can include batch orcontinuous processes. Continuous processes can use intermittent orcontinuous product discharge. Processes can also include partial or fulldirect recycle of unreacted monomer, unreacted comonomer, and/ordiluent.

Polymerization reactor systems of the present invention can comprise onetype of reactor in a system or multiple reactors of the same ordifferent type (e.g., a single reactor, dual reactor, more than tworeactors). Production of polymers in multiple reactors can includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorscan be different from the operating conditions of the other reactor(s).Alternatively, polymerization in multiple reactors can include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems can include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors canbe operated in series, in parallel, or both. Accordingly, the presentinvention encompasses polymerization reactor systems comprising a singlereactor, comprising two reactors, and comprising more than two reactors.The polymerization reactor system can comprise a slurry reactor, agas-phase reactor, a solution reactor, in certain embodiments of thisinvention, as well as multi-reactor combinations thereof.

According to one embodiment of the invention, the polymerization reactorsystem can comprise at least one loop slurry reactor comprising verticalor horizontal loops. Monomer, diluent, catalyst, and comonomer can becontinuously fed to a loop reactor where polymerization occurs.Generally, continuous processes can comprise the continuous introductionof monomer/comonomer, a catalyst, and a diluent into a polymerizationreactor and the continuous removal from this reactor of a suspensioncomprising polymer particles and the diluent. Reactor effluent can beflashed to remove the solid polymer from the liquids that comprise thediluent, monomer and/or comonomer. Various technologies can be used forthis separation step including, but not limited to, flashing that caninclude any combination of heat addition and pressure reduction,separation by cyclonic action in either a cyclone or hydrocyclone, orseparation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415,each of which is incorporated herein by reference in its entirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under polymerization conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used. An example is polymerization ofpropylene monomer as disclosed in U.S. Pat. Nos. 5,455,314, which isincorporated by reference herein in its entirety.

According to yet another embodiment of this invention, thepolymerization reactor system can comprise at least one gas phasereactor. Such systems can employ a continuous recycle stream containingone or more monomers continuously cycled through a fluidized bed in thepresence of the catalyst under polymerization conditions. A recyclestream can be withdrawn from the fluidized bed and recycled back intothe reactor. Simultaneously, polymer product can be withdrawn from thereactor and new or fresh monomer can be added to replace the polymerizedmonomer. Such gas phase reactors can comprise a process for multi-stepgas-phase polymerization of olefins, in which olefins are polymerized inthe gaseous phase in at least two independent gas-phase polymerizationzones while feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and5,436,304, each of which is incorporated by reference in its entiretyherein.

According to still another embodiment of the invention, a high pressurepolymerization reactor can comprise a tubular reactor or an autoclavereactor. Tubular reactors can have several zones where fresh monomer,initiators, or catalysts are added. Monomer can be entrained in an inertgaseous stream and introduced at one zone of the reactor. Initiators,catalysts, and/or catalyst components can be entrained in a gaseousstream and introduced at another zone of the reactor. The gas streamscan be intermixed for polymerization. Heat and pressure can be employedappropriately to obtain optimal polymerization reaction conditions.

According to yet another embodiment of the invention, the polymerizationreactor system can comprise a solution polymerization reactor whereinthe monomer (and comonomer, if used) are contacted with the catalystcomposition by suitable stirring or other means. A carrier comprising aninert organic diluent or excess monomer can be employed. If desired, themonomer/comonomer can be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation can be employed to obtain bettertemperature control and to maintain uniform polymerization mixturesthroughout the polymerization zone. Adequate means are utilized fordissipating the exothermic heat of polymerization.

Polymerization reactor systems suitable for the present invention canfurther comprise any combination of at least one raw material feedsystem, at least one feed system for catalyst or catalyst components,and/or at least one polymer recovery system. Suitable reactor systemsfor the present invention can further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Polymerization conditions that are controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. A suitable polymerization temperature canbe any temperature below the de-polymerization temperature according tothe Gibbs Free energy equation. Typically, this includes from about 60°C. to about 280° C., for example, or from about 60° C. to about 120° C.,depending upon the type of polymerization reactor(s). In some reactorsystems, the polymerization temperature generally can fall within arange from about 70° C. to about 100° C., or from about 75° C. to about95° C. Various polymerization conditions can be held substantiallyconstant, for example, for the production of a particular grade ofolefin polymer.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig (6.9 MPa). Pressure forgas phase polymerization is usually at about 200 to 500 psig (1.4 MPa to3.4 MPa). High pressure polymerization in tubular or autoclave reactorsis generally run at about 20,000 to 75,000 psig (138 to 517 MPa).Polymerization reactors can also be operated in a supercritical regionoccurring at generally higher temperatures and pressures. Operationabove the critical point of a pressure/temperature diagram(supercritical phase) may offer advantages.

Embodiments of this invention are directed to olefin polymerizationprocesses comprising contacting a catalyst composition with an olefinmonomer and an optional olefin comonomer in a polymerization reactorsystem under polymerization conditions to produce an olefin polymer. Theolefin polymer (e.g., ethylene copolymer) produced by the process canhave any of the polymer properties disclosed herein.

Embodiments of this invention also are directed to olefin polymerizationprocesses conducted in the absence of added hydrogen. An olefinpolymerization process of this invention can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer, wherein the catalystcomposition can comprise catalyst component I, catalyst component II, anactivator, and an optional co-catalyst, and wherein the polymerizationprocess is conducted in the absence of added hydrogen (no hydrogen isadded to the polymerization reactor system). As one of ordinary skill inthe art would recognize, hydrogen can be generated in-situ bymetallocene catalyst compositions in various olefin polymerizationprocesses, and the amount generated can vary depending upon the specificcatalyst composition and metallocene compound(s) employed, the type ofpolymerization process used, the polymerization reaction conditionsutilized, and so forth.

In other embodiments, it may be desirable to conduct the polymerizationprocess in the presence of a certain amount of added hydrogen.Accordingly, an olefin polymerization process of this invention cancomprise contacting a catalyst composition with an olefin monomer andoptionally an olefin comonomer in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition comprises catalyst component I, catalyst componentII, an activator, and an optional co-catalyst, and wherein thepolymerization process is conducted in the presence of added hydrogen(hydrogen is added to the polymerization reactor system). For example,the ratio of hydrogen to the olefin monomer in the polymerizationprocess can be controlled, often by the feed ratio of hydrogen to theolefin monomer entering the reactor. The added hydrogen to olefinmonomer ratio in the process can be controlled at a weight ratio whichfalls within a range from about 25 ppm to about 1500 ppm, from about 50to about 1000 ppm, or from about 100 ppm to about 750 ppm.

In some embodiments of this invention, the feed or reactant ratio ofhydrogen to olefin monomer can be maintained substantially constantduring the polymerization run for a particular polymer grade. That is,the hydrogen:olefin monomer ratio can be selected at a particular ratiowithin a range from about 5 ppm up to about 1000 ppm or so, andmaintained at the ratio to within about +/−25% during the polymerizationrun. For instance, if the target ratio is 100 ppm, then maintaining thehydrogen:olefin monomer ratio substantially constant would entailmaintaining the feed ratio between about 75 ppm and about 125 ppm.Further, the addition of comonomer (or comonomers) can be, and generallyis, substantially constant throughout the polymerization run for aparticular polymer grade.

However, in other embodiments, it is contemplated that monomer,comonomer (or comonomers), and/or hydrogen can be periodically pulsed tothe reactor, for instance, in a manner similar to that employed in U.S.Pat. No. 5,739,220 and U.S. Patent Publication No. 2004/0059070, thedisclosures of which are incorporated herein by reference in theirentirety.

The concentration of the reactants entering the polymerization reactorsystem can be controlled to produce resins with certain physical andmechanical properties. The proposed end-use product that will be formedby the polymer resin and the method of forming that product ultimatelycan determine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to, and encompasses, the polymersproduced by any of the polymerization processes disclosed herein.Articles of manufacture can be formed from, and/or can comprise, thepolymers produced in accordance with this invention.

Polymers and Articles

Olefin polymers encompassed herein can include any polymer produced fromany olefin monomer and comonomer(s) described herein. For example, theolefin polymer can comprise an ethylene homopolymer, a propylenehomopolymer, an ethylene copolymer (e.g., ethylene/α-olefin,ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, etc.), apropylene copolymer, an ethylene terpolymer, a propylene terpolymer, andthe like, including combinations thereof. In one embodiment, the olefinpolymer can be an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, or an ethylene/1-octene copolymer, while in anotherembodiment, the olefin polymer can be an ethylene/1-hexene copolymer.

If the resultant polymer produced in accordance with the presentinvention is, for example, an ethylene polymer, its properties can becharacterized by various analytical techniques known and used in thepolyolefin industry. Articles of manufacture can be formed from, and/orcan comprise, the ethylene polymers of this invention, whose typicalproperties are provided below.

In particular embodiments and unexpectedly, the polymers disclosedherein often can have a majority of the LCB in a lower molecular weightcomponent of the polymer (a ratio of the number of LCB of the lowermolecular weight component to the number of LCB of the higher molecularweight component, per millions total carbon atoms, typically can be in arange from about 4:1 to about 100:1, or from about 5:1 to about 50:1,e.g., about 8:1, about 10:1, about 15:1, about 20:1, etc.), a majorityof the SCB in a higher molecular weight component of the polymer, and aratio of the Mp of the higher molecular weight component to the Mp ofthe lower molecular weight component in particular ranges. Anillustrative and non-limiting example of an olefin polymer (e.g., anethylene copolymer) consistent with embodiments of this invention cancomprise a higher molecular weight component and a lower molecularweight component, and can be characterized as having the followingproperties: a ratio of the Mp of the higher molecular weight componentto the Mp of the lower molecular weight component in a range from about5:1 to about 100:1, a number of LCB of the lower molecular weightcomponent in a range from about 5 to about 50 LCB per million totalcarbon atoms, and a number of LCB of the higher molecular weightcomponent of less than or equal to about 5 LCB per million total carbonatoms. Another illustrative and non-limiting ethylene-based polymerdescribed herein can have a lower molecular weight component having a Mpin a range from about 15 to about 80 kg/mol, and from about 5 to about50 LCB per million total carbon atoms, and a higher molecular weightcomponent having a Mp in a range from about 150 to about 800 kg/mol, andless than or equal to about 5 LCB per million total carbon atoms. Yetanother illustrative and non-limiting ethylene-based polymer describedherein can have a ratio of the Mp of the higher molecular weightcomponent to the Mp of the lower molecular weight component in a rangefrom about 5:1 to about 100:1, and a ratio of the number of LCB of thepolymer to the number of LCB of the higher molecular weight component,per millions total carbon atoms, in a range from about 2:1 to about100:1. And yet another illustrative and non-limiting ethylene-basedpolymer described herein can have a ratio of the Mp of the highermolecular weight component to the Mp of the lower molecular weightcomponent in a range from about 5:1 to about 100:1, a number of LCB ofthe higher molecular weight component of less than or equal to about 5LCB per million total carbon atoms, and a number of LCB of the olefinpolymer in a range from about 2 to about 30 LCB per million total carbonatoms. These illustrative and non-limiting examples of olefin polymers(e.g., ethylene α-olefin copolymers) consistent with the presentinvention also can have any of the polymer properties listed below andin any combination.

Polymers of ethylene (homopolymer, copolymers, etc.) produced inaccordance with some embodiments of this invention generally can have amelt index (MI) of less than or equal to about 2 g/10 min. Melt indicesin the range from 0 to about 1 g/10 min, from 0 to about 0.4 g/10 min,or from 0 to about 0.3 g/10 min, are contemplated in other embodimentsof this invention. For example, a polymer of the present invention canhave a melt index in a range from 0 to about 0.25, or from 0 to about0.2 g/10 min. In an embodiment, ethylene polymers described herein canhave a high load melt index (HLMI) in a range from about 3 to about 60,from about 4 to about 30, or from about 4 to about 25 g/10 min. Inanother embodiment, ethylene polymers described herein can have a HLMIin a range from about 3 to about 25, from about 3 to about 20, fromabout 4 to about 20, from about 5 to about 18, or from about 5 to about15 g/10 min. In particular embodiments, ethylene polymers describedherein can have a ratio of HLMI/MI in a range from about 50 to about300, from about 100 to about 350, from about 150 to about 300, fromabout 180 to about 350, from about 60 to about 250, from about 60 toabout 200, or from about 70 to about 225.

The densities of ethylene-based polymers produced using the catalystsystems and processes disclosed herein often are less than or equal toabout 0.94 g/cm³. In one embodiment of this invention, the density ofthe ethylene polymer can be in a range from about 0.91 to about 0.94g/cm³. Yet, in another embodiment, the density can be in a range fromabout 0.915 to about 0.935, from about 0.913 to about 0.93, from about0.917 to about 0.928, or from about 0.92 to about 0.928 g/cm³.

In an embodiment, ethylene polymers described herein can have a ratio ofMw/Mn, or the polydispersity index, in a range from about 6 to about 50,such as, for example, from about 8 to about 35, from about 10 to about35, or from about 12 to about 50. In another embodiment, ethylenepolymers described herein can have a Mw/Mn in a range from about 14 toabout 35, from about 6 to about 20, or from about 8 to about 16.

In an embodiment, ethylene polymers described herein can have a ratio ofMz/Mw in a range from about 3 to about 12. For instance, the Mz/Mw canbe in a range from about 3 to about 6, from about 3.5 to about 9, orfrom about 3.5 to about 6.

In an embodiment, ethylene polymers described herein can have aweight-average molecular weight (Mw) in a range from about 100 to about600, from about 175 to about 600, or from about 120 to about 500 kg/mol.Other suitable ranges for Mw can include, but are not limited to, fromabout 190 to about 500, from about 120 to about 300, from about 150 toabout 350 kg/mol, and the like.

In an embodiment, ethylene polymers described herein can have anumber-average molecular weight (Mn) in a range from about 8 to about60, or from about 10 to about 50 kg/mol. Other suitable ranges for Mncan include, but are not limited to, from about 10 to about 25, fromabout 12 to about 45 kg/mol, from about 13 to about 23 kg/mol, and thelike.

In an embodiment, ethylene polymers described herein can have a CY-aparameter at 190° C. in a range from about 0.2 to about 0.45, from about0.25 to about 0.4, from about 0.25 to about 0.38, or from about 0.25 toabout 0.35. Additionally or alternatively, ethylene polymers describedherein can have a zero-shear viscosity at 190° C. in a range from about10,000 to about 500,000, from about 60,000 to about 500,000, from about20,000 to about 400,000, from about 70,000 to about 400,000, or fromabout 30,000 to about 300,000 Pa-sec. Additionally or alternatively,ethylene polymers described herein can have a Tau(η) at 190° C. in arange from about 0.1 to about 3, from about 0.6 to about 3, from about 1to about 3, from about 0.2 to about 2, or from about 0.4 to about 2 sec.

Ethylene copolymers, for example, produced using the polymerizationprocesses and catalyst systems described hereinabove can, in someembodiments, have a reverse comonomer distribution, generally, thehigher molecular weight components of the polymer have higher comonomerincorporation than the lower molecular weight components. Typically,there is increasing comonomer incorporation with increasing molecularweight. In one embodiment, the number of short chain branches (SCB) per1000 total carbon atoms of the polymer can be greater at Mw than at Mn.In another embodiment, the number of SCB per 1000 total carbon atoms ofthe polymer can be greater at Mz than at Mw. In yet another embodiment,the number of SCB per 1000 total carbon atoms of the polymer can begreater at Mz than at Mn. In still another embodiment, a ratio of thenumber of SCB per 1000 total carbon atoms of the polymer at Mz to thenumber of SCB per 1000 total carbon atoms of the polymer at Mn can be ina range from about 1.1 to about 5, such as, for example, from about 1.2to about 4, or from about 1.2 to about 2.5.

As described herein, olefin polymers (e.g., ethylene copolymers) canhave a lower molecular weight component and a higher molecular weightcomponent. The peak molecular weight (Mp) for the lower molecular weightcomponent and the Mp for the higher molecular weight component aredetermined by deconvoluting the composite (overall polymer) molecularweight distribution (which was determined using gel permeationchromatography). As described herein, the number of long chain branches(LCB) in the lower molecular weight component and the number of LCB inthe higher molecular weight component are determined by performing apolymerization experiment for each catalyst component separately (e.g.,a two carbon bridged metallocene compound having formula (A) or a singleatom bridged metallocene compound having formula (B)) to produce apolymer having a Mw in the 100-125 kg/mol range, and then applying theJanzen-Colby method for determining the number of LCB per million carbonatoms.

The amount of the higher molecular weight component, based on the totalpolymer, is not limited to any particular range. Generally, however, theamount of the higher molecular weight component can be in a range fromabout 10 to about 60 area %, from about 15 to about 50 area %, fromabout 20 to about area 55%, from about 20 to about 45 area %, or fromabout 20 to about area 40%, based on the amount of the total polymer,determined by deconvoluting the polymer MWD to determine the amounts ofthe lower molecular weight component and the higher molecular weightcomponent.

Ethylene polymers, such as homopolymers, copolymers, etc., consistentwith various embodiments of the present invention generally can have aratio of the Mp of the higher molecular weight component to the Mp ofthe lower molecular weight component in a range from about 2:1 to about100:1, or from about 5:1 to about 100:1. For instance, this ratio can bein a range from about 5:1 to about 30:1, from about 7:1 to about 50:1,from about 8:1 to about 25:1, or from about 7:1 to about 20:1.

In an embodiment, ethylene polymers described herein can have a Mp ofthe lower molecular weight component in a range from about 10 to about100, from about 15 to about 80, or from about 20 to about 70 kg/mol.Other suitable ranges for Mp of the lower molecular weight component caninclude, but are not limited to, from about 30 to about 60, from about18 to about 50, from about 18 to about 35 kg/mol, and the like.

In an embodiment, ethylene polymers described herein can have a Mp ofthe higher molecular weight component in a range from about 200 to about1,000, from about 150 to about 800, or from about 200 to about 700kg/mol. Other suitable ranges for Mp of the higher molecular weightcomponent can include, but are not limited to, from about 150 to about500 kg/mol, from about 200 to about 500 kg/mol, from about 175 to about300 kg/mol, and the like.

Ethylene polymers consistent with various embodiments of the presentinvention generally can have a ratio of the number of LCB of the olefinpolymer to the number of LCB of the higher molecular weight component,per million total carbon atoms, in a range from about 2:1 to about100:1, from about 3:1 to about 50:1, or from about 2:1 to about 25:1.For instance, this ratio can be in a range from about 2:1 to about 10:1,from about 3:1 to about 15:1, from about 5:1 to about 10:1, or fromabout 7:1 to about 10:1.

In an embodiment, ethylene polymers described herein can have a numberof LCB of the lower molecular weight component in a range from about 5to about 100, from about 5 to about 50, from about 8 to about 30, fromabout 5 to about 15, or from about 5 to about 10 LCB per million totalcarbon atoms. Additionally or alternatively, the number of LCB of thehigher molecular weight component of the polymer can be less than orequal to about 10 LCB, less than or equal to about 5 LCB, less than orequal to about 3 LCB, less than or equal to about 2 LCB, or less than orequal to about 1 LCB per million total carbon atoms. Additionally oralternatively, the number of LCB of the olefin polymer can be in a rangefrom about 1 to about 50, from about 1 to about 30, from about 2 toabout 20, from about 1 to about 10, or from about 3 to about 12 LCB permillion total carbon atoms.

Articles of manufacture can be formed from, and/or can comprise, theolefin polymers (e.g., ethylene copolymers) of this invention and,accordingly, are encompassed herein. For example, articles which cancomprise polymers of this invention can include, but are not limited to,an agricultural film, an automobile part, a bottle, a drum, a fiber orfabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, a pipe, a sheet or tape, a toy,and the like. Various processes can be employed to form these articles.Non-limiting examples of these processes include injection molding, blowmolding, rotational molding, film extrusion, sheet extrusion, profileextrusion, thermoforming, and the like. Additionally, additives andmodifiers are often added to these polymers in order to providebeneficial polymer processing or end-use product attributes. Suchprocesses and materials are described in Modern Plastics Encyclopedia,Mid-November 1995 Issue, Vol. 72, No. 12; and Film ExtrusionManual—Process, Materials, Properties, TAPPI Press, 1992; thedisclosures of which are incorporated herein by reference in theirentirety.

In some embodiments, the article produced from and/or comprising apolymer of this invention is a film product. For instance, the film canbe a blown film or a cast film that is produced from and/or comprisesany of the olefin polymers disclosed herein. Such films also can containone or more additives, non-limiting examples of which can include anantioxidant, an acid scavenger, an antiblock additive, a slip additive,a colorant, a filler, a processing aid, a UV inhibitor, and the like, aswell as combinations thereof.

Applicants also contemplate a method for forming or preparing an articleof manufacture comprising a polymer produced by any of thepolymerization processes disclosed herein. For instance, a method cancomprise (i) contacting a catalyst composition with an olefin monomerand an optional olefin comonomer under polymerization conditions in apolymerization reactor system to produce an olefin polymer, wherein thecatalyst composition can comprise catalyst component I, catalystcomponent II, an activator (e.g., an activator-support comprising asolid oxide treated with an electron-withdrawing anion), and an optionalco-catalyst (e.g., an organoaluminum compound); and (ii) forming anarticle of manufacture comprising the olefin polymer. The forming stepcan comprise blending, melt processing, extruding, molding, orthermoforming, and the like, including combinations thereof.

Applicants also contemplate a method for making a film (e.g., a blownfilm, a cast film, etc.) comprising any olefin polymer disclosed herein.For instance, the method can comprise melt processing the olefin polymerthrough a die to form the film. Suitably, the die can be configuredbased on the film to be produced, for example, an annular blown film dieto produce a blown film, a slot or cast film die to produce a cast film,and so forth. Moreover, any suitable means of melt processing can beemployed, although extrusion typically can be utilized. As above,additives can be combined with the polymer in the melt processing step(extrusion step), such as antioxidants, acid scavengers, antiblockadditives, slip additives, colorants, fillers, processing aids, UVinhibitors, and the like, as well as combinations thereof.

Films disclosed herein, whether cast or blown, can be any thickness thatis suitable for the particular end-use application, and often, the filmthickness can be in a range from about 0.25 to about 250 mils, or fromabout 0.4 to about 100 mils. For thin film applications, typicalthicknesses can be in a range from about 0.25 to about 10 mils, fromabout 0.4 to about 5 mils, from about 0.5 to about 2 mils, or from about0.5 to about 1.5 mils.

In an embodiment and unexpectedly, the films disclosed herein (e.g.,blown films) can have a high dart impact strength (at a low melt index).Further, such films also can have relatively high haze and shrink, andlow COF properties, as compared to conventional blown films of generallythe same nominal density. For instance, a blown film consistent withembodiments of this invention can comprise an olefin polymer having amelt index less than or equal to about 0.4 g/10 min, and the blown film(produced under LLDPE and/or HDPE conditions) can have a dart impactstrength greater than or equal to about 300 g/mil. In some embodiments,the film (produced under LLDPE and/or HDPE conditions) can have a dartimpact strength in a range from about 300 to about 2000, from about 400to about 2000, from about 500 to about 2000, from about 600 to about2000, or from about 700 to about 2000 g/mil.

The olefin polymer, for example, an ethylene a-olefin copolymer, used toproduce such films can be further characterized by any of the polymerproperties listed above and in any combination. As a non-limitingexample, the olefin polymer can have a MI of less than or equal to about0.4, less than or equal to about 0.3, less than or equal to about 0.25,or less than or equal to about 0.2 g/10 min. Additionally oralternatively, the olefin polymer can have a density from about 0.91 toabout 0.94, from about 0.915 to about 0.935, from about 0.913 to about0.93, from about 0.917 to about 0.928, or from about 0.92 to about 0.928g/cm³. Additionally or alternatively, the olefin polymer can becharacterized by a HLMI in a range from about 3 to about 60, from about4 to about 30, from about 4 to about 25, from about 4 to about 20, fromabout 5 to about 18, or from about 5 to about 15 g/10 min; and/or by aMw/Mn in a range from about 6 to about 50, from about 8 to about 35,from about 10 to about 35, from about 12 to about 50, from about 14 toabout 35, from about 6 to about 20, or from about 8 to about 16.

In an embodiment, film products of this invention also can becharacterized by relatively high haze and relatively low coefficient offriction (COF) properties, i.e., in the absence of any additives thatmight impact such measurements, for example, slip and antiblockadditives. Representative blown films described herein (produced underLLDPE and/or HDPE conditions) can have a film haze of greater than orequal to about 55, greater than or equal to about 65, greater than orequal to about 75, greater than or equal to about 80, or greater than orequal to about 85%, and often the film haze can range up to 95-98%.Likewise, representative blown films described herein (produced underLLDPE and/or HDPE conditions) can have a kinetic COF in a range fromabout 0.3 to about 0.5, from about 0.3 to about 0.48, from about 0.32 toabout 0.47, or from about 0.3 to about 0.42.

In an embodiment, 1-mil blown films described herein (produced underLLDPE and/or HDPE conditions) can have a MD shrink at 250° F. in a rangefrom about 20 to about 70, from about 35 to about 70, or from about 25to about 65%. Other suitable ranges for MD shrink of the 1-mil film at250° F. can include, but are not limited to, from about 27 to about 65%,from about 30 to about 60%, and the like.

In another embodiment, blown films described herein (produced underLLDPE and/or HDPE conditions) can be characterized by the MD Elmendorftear strength. Suitable ranges can include, but are not limited to, fromabout 10 to about 150, from about 25 to about 150, from about 50 toabout 150, or from about 75 to about 150 g/mil.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2,160 gram weight. High load melt index (HLMI, g/10min) was determined in accordance with ASTM D1238 at 190° C. with a21,600 gram weight.

Polymer density was determined in grams per cubic centimeter (g/cm³) ona compression molded sample, cooled at about 15° C. per hour, andconditioned for about 40 hours at room temperature in accordance withASTM D1505 and ASTM D4703.

Molecular weights and molecular weight distributions were obtained usinga PL-GPC 220 (Polymer Labs, an Agilent Company) system equipped with aIR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns(Waters, MA) running at 145° C. The flow rate of the mobile phase1,2,4-trichlorobenzene (TCB) containing 0.5 g/L2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 mL/min, and polymersolution concentrations were in the range of 1.0-1.5 mg/mL, depending onthe molecular weight. Sample preparation was conducted at 150° C. fornominally 4 hr with occasional and gentle agitation, before thesolutions were transferred to sample vials for injection. An injectionvolume of about 200 μL was used. The integral calibration method wasused to deduce molecular weights and molecular weight distributionsusing a Chevron Phillips Chemicals Company's HDPE polyethylene resin,MARLEX® BHB5003, as the broad standard. The integral table of the broadstandard was pre-determined in a separate experiment with SEC-MALS. Mnis the number-average molecular weight, Mw is the weight-averagemolecular weight, Mz is the z-average molecular weight, and Mp is thepeak molecular weight.

Melt rheological characterizations were performed as follows.Small-strain (10%) oscillatory shear measurements were performed on aRheometrics Scientific, Inc. ARES rheometer using parallel-plategeometry. All rheological tests were performed at 190° C. The complexviscosity |η*| versus frequency (ω) data were then curve fitted usingthe modified three parameter Carreau-Yasuda (CY) empirical model toobtain the zero shear viscosity—η₀, characteristic viscous relaxationtime—τ_(η), and the breadth parameter—α. The simplified Carreau-Yasuda(CY) empirical model is as follows.

${{{\eta*(\omega)}} = \frac{\eta_{0}}{\left\lbrack {1 + \left( {\tau_{\eta}\omega} \right)^{a}} \right\rbrack^{{({1 - n})}/a}}},$

wherein: |η*(ω)|=magnitude of complex shear viscosity;

-   -   η₀=zero shear viscosity;    -   τ_(η)=viscous relaxation time (Tau(η));    -   α=“breadth” parameter (CY-a parameter);    -   n=fixes the final power law slope, fixed at 2/11; and    -   ω=angular frequency of oscillatory shearing deformation.

Details of the significance and interpretation of the CY model andderived parameters may be found in: C. A. Hieber and H. H. Chiang,Rheol. Acta, 28, 321 (1989); C. A. Hieber and H. H. Chiang, Polym. Eng.Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger,Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition,John Wiley & Sons (1987); each of which is incorporated herein byreference in its entirety.

The long chain branches (LCB) per 1,000,000 total carbon atoms werecalculated using the method of Janzen and Colby (J. Mol. Struct.,485/486, 569-584 (1999)), from values of zero shear viscosity, η_(o)(determined from the Carreau-Yasuda model, described hereinabove), andmeasured values of Mw obtained using a Dawn EOS multiangle lightscattering detector (Wyatt). See also U.S. Pat. No. 8,114,946; J. Phys.Chem. 1980, 84, 649; and Y. Yu, D. C. Rohlfing, G. R Hawley, and P. J.DesLauriers, Polymer Preprints, 44, 49-50 (2003). These references areincorporated herein by reference in their entirety.

Short chain branch (SCB) content and short chain branching distribution(SCBD) across the molecular weight distribution were determined via anIRS-detected GPC system (IR5-GPC), wherein the GPC system was a PL220GPC/SEC system (Polymer Labs, an Agilent company) equipped with threeStyragel HMW-6E columns (Waters, Mass.) for polymer separation. Athermoelectric-cooled IRS MCT detector (IR5) (Polymer Char, Spain) wasconnected to the GPC columns via a hot-transfer line. Chromatographicdata were obtained from two output ports of the IRS detector. First, theanalog signal goes from the analog output port to a digitizer beforeconnecting to Computer “A” for molecular weight determinations via theCirrus software (Polymer Labs, now an Agilent Company) and the integralcalibration method using a broad MWD HDPE Marlex™ BHB5003 resin (ChevronPhillips Chemical) as the broad molecular weight standard. The digitalsignals, on the other hand, go via a USB cable directly to Computer “B”where they are collected by a LabView data collection software providedby Polymer Char. Chromatographic conditions were set as follows: columnoven temperature of 145° C.; flowrate of 1 mL/min; injection volume of0.4 mL; and polymer concentration of about 2 mg/mL, depending on samplemolecular weight. The temperatures for both the hot-transfer line andIRS detector sample cell were set at 150° C., while the temperature ofthe electronics of the IRS detector was set at 60° C. Short chainbranching content was determined via an in-house method using theintensity ratio of CH₃ (I_(CH3)) to CH₂ (I_(CH2)) coupled with acalibration curve. The calibration curve was a plot of SCB content(x_(SCB)) as a function of the intensity ratio of I_(CH3)/I_(CH2). Toobtain a calibration curve, a group of polyethylene resins (no less than5) of SCB level ranging from zero to ca. 32 SCB/1,000 total carbons (SCBStandards) were used. All these SCB Standards have known SCB levels andflat SCBD profiles pre-determined separately by NMR and thesolvent-gradient fractionation coupled with NMR (SGF-NMR) methods. UsingSCB calibration curves thus established, profiles of short chainbranching distribution across the molecular weight distribution wereobtained for resins fractionated by the IR5-GPC system under exactly thesame chromatographic conditions as for these SCB standards. Arelationship between the intensity ratio and the elution volume wasconverted into SCB distribution as a function of MWD using apredetermined SCB calibration curve (i.e., intensity ratio ofI_(CH3)/I_(CH2) vs. SCB content) and MW calibration curve (i.e.,molecular weight vs. elution time) to convert the intensity ratio ofI_(CH3)/I_(CH2) and the elution time into SCB content and the molecularweight, respectively.

Pilot plant polymerizations were conducted in a 23-gallon slurry loopreactor at a production rate of approximately 25 pounds of polymer perhour. Polymerization runs were carried out under continuous particleform process conditions in a loop reactor (also known as a slurryprocess) by contacting a dual metallocene solution in isobutane, anorganoaluminum solution, and an activator-support in a 1-L stirredautoclave with continuous output to the loop reactor. The organoaluminumand dual metallocene solutions were fed as separate streams into a teeupstream of the autoclave where they contacted each other. Theactivator-support was flushed with isobutane into a tee between theaforementioned tee and the autoclave, contacting theorganoaluminum/metallocene mixture just before entering the autoclave.The isobutane flush used to transport the activator-support into theautoclave was set at a rate that would result in a residence time ofapproximately 25 minutes in the autoclave. The total flow from theautoclave then entered the loop reactor.

Ethylene used was polymerization grade ethylene which was purifiedthrough a column of alumina (activated at 250° C. in nitrogen). 1-Hexenewas polymerization grade 1-hexene (obtained from Chevron PhillipsChemical Company) which was purified by nitrogen purging and storageover 13-X molecular sieve activated at 250° C. (482° F.) in nitrogen.The loop reactor was a liquid full, 15.2 cm diameter, loop reactor,having a volume of 23 gallons (87 liters). Liquid isobutane was used asthe diluent. Hydrogen was added to regulate the molecular weight and/orHLMI of the polymer product. The isobutane was polymerization gradeisobutane (obtained from Chevron Phillips Chemical Company) that wasfurther purified by distillation and subsequently passed through acolumn of alumina (activated at 250° C. in nitrogen).

Reactor conditions included a pressure around 580 psi (4 MPa), and atemperature that was varied from about 70° C. (158° F.) to about 100° C.(212° F.) as indicated in the examples. Also, the reactor was operatedto have a residence time of about 1.25 hr. Metallocene concentrations inthe reactor were within a range of about 1 to 2 parts per million (ppm)of the diluent in the polymerization reactor. Polymer was removed fromthe reactor at the rate of about 25 lb/hr and recovered in a flashchamber. A Vulcan dryer was used to dry the polymer under nitrogen atabout 60-80° C.

Cocatalyst tri-isobutylaluminum (TIBA, obtained from Akzo Corporation)was also used. The cocatalyst was obtained as a one molar solution inheptane, but was further diluted to 1 weight percent. The cocatalyst wasadded in a concentration in a range of from about 50 to 60 parts permillion of the diluent in the polymerization reactor. To prevent staticbuildup of the reactor, a small amount (less than 5 ppm, by weight, ofdiluent) of a commercial antistatic agent sold as “Stadis 450” was addedas needed.

Metallocene A was rac-ethylene-bis(indenyl) zirconium dichloride, andMetallocene B wasdiphenylmethylidene{η⁵-[3-(penten-4-yl)cyclopentadien-1-ylidene]}[η⁵-(2,7-di-tert-butylfluoren-9-ylidene)]zirconium dichloride.

Fluorided silica-coated aluminas were prepared as follows. Alumina A,from W.R. Grace Company, was impregnated to incipient wetness was firstcalcined in dry air at about 600° C. for approximately 6 hours, cooledto ambient temperature, and then contacted with tetraethylorthosilicatein isopropanol to equal 25 wt. % SiO₂. After drying, the silica-coatedalumina was calcined at 600° C. for 3 hours. Fluorided silica-coatedalumina (7 wt. % F) was prepared by impregnating the calcinedsilica-coated alumina with an ammonium bifluoride solution in methanol,drying, and then calcining for 3 hours at 600° C. (unless otherwisenoted) in dry air. Afterward, the fluorided silica-coated alumina wascollected and stored under dry nitrogen, and was used without exposureto the atmosphere.

Some of the blown film samples were made on a laboratory-scale blownfilm line using typical linear low density polyethylene conditions(LLDPE) as follows: 100 mm (4 inch) die diameter, 1.5 mm (0.060 inch)die gap, 37.5 mm (1.5 inch) diameter single-screw extruder fitted with abarrier screw with a Maddock mixing section at the end (L/D=24, 2.2:1compression ratio), about 27 kg/hr (60 lb/hr) output rate, 2.5:1 blow-upratio (BUR), “in-pocket” bubble with a “frost line height” (FLH) ofabout 28 cm (11 inch), 190° C. (375° F.) barrel and die settemperatures, and 1 mil (25 micron) film and 3 mil (75 micron) film.Cooling was accomplished with a Dual Lip air ring using ambient(laboratory) air at about 25° C. (75-80° F.). These particularprocessing conditions were chosen because the film properties soobtained are typically representative of those obtained from larger,commercial scale film blowing conditions.

Other blown film samples were made on the same film line, but under highdensity polyethylene conditions (HDPE). Typically, the copolymer wasblown into a 1 mil film on a 2-inch die, with a 35-mil die gap, at 205°C./220° C. barrel/die set temperatures, at a rate of 28-30 lb/hr, with a4:1 blow-up ratio, and a 14 inch frost line height.

Dart impact strength was measured in accordance with ASTM D-1709 (methodA). Machine (MD) and transverse (TD) direction Elmendorf tear strengthswere measured on a Testing Machines Inc. tear tester (Model 83-11-00) inaccordance with ASTM D-1922. Film haze was determined in accordance withASTM D1003, film-to-film coefficient of friction (COF) was determined inaccordance with ASTM D1894, film shrink properties were determined inaccordance with ASTM D2732, and Spencer Impact was determined inaccordance with ASTM D3420.

EXAMPLES 1-9

Example 1 was a broad monomodal LLDPE film resin, having a nominal 0.2melt index and 0.924 density, commercially available fromChevron-Phillips Chemical Company LP. Each of Examples 2-9 utilized adual catalyst system containing a two carbon bridged, zirconium basedmetallocene compound containing two indenyl groups (Metallocene A) and asingle atom bridged, zirconium based metallocene compound containing acyclopentadienyl and a fluorenyl group (Metallocene B).

In Example 2, bimodal polymer was produced in the reactor describedabove using a solution containing Metallocenes A and B at an A:B weightratio of 8:1. The total metallocene concentration in the reactor was 0.8ppm by weight, and the activator-support (fluorided silica-coatedalumina, described above) was fed to the reactor at the rate ofapproximately 0.25 lb per hour, to achieve a yield of about 2000 lbpolymer per lb of the fluorided silica-coated aluminaTriisobutylaluminum was fed to the reactor to maintain a concentrationof 50 ppm by weight in the isobutane. 1-Hexene was added to the reactorto maintain a concentration of about 2.5 mol %, and ethylene was addedto maintain a concentration of about 12 mol % (based on the isobutanediluent). About 4.5 mlb of hydrogen were added to the reactor per hour.Reactor temperature was set at 79-80° C., the reactor residence time wasabout 1.2 hr, and the reactor % solids were 29.4-30.3%. Examples 3-9were produced in the same manner as Example 2, generally at 11.4-12.4mol % ethylene and 2.5-2.9 mol % 1-hexene, and with the followingdifferent amounts of the metallocene catalysts: Example 3 (1.12 ppm ofmetallocenes at a 12:1 weight ratio of A:B), Example 4 (0.92 ppm ofmetallocenes at a 8:1 weight ratio of A:B), Example 5 (1.02 ppm ofmetallocenes at a 20:1 weight ratio of A:B), Example 6 (1.6 ppm ofmetallocenes at a 20:1 weight ratio of A:B), Example 7 (0.83 ppm ofmetallocenes at a 20:1 weight ratio of A:B), Example 8 (0.79 ppm ofmetallocenes at a 20:1 weight ratio of A:B), and Example 9 (0.66 ppm ofmetallocenes at a 30:1 weight ratio of A:B)

Table I summarizes the polymer properties of Examples 1-9. For instance,the polymers of Examples 2-7 exhibited a unique combination of density,Mw/Mn, HLMI, LCB content, and SCB distribution. The broad molecularweight distribution and reverse comonomer distribution of the polymersproduced using the dual metallocene-based catalyst systems disclosedherein are illustrated in FIGS. 1-8 for the polymers of Examples 2-9,respectively (e.g., there are relatively more short chain branches (SCB)at the higher molecular weights; assumes 2 methyl chain ends (CE)). InFIGS. 1-8, the number of SCB per 1000 total carbon (TC) atoms of thepolymer at Mz (or Mw) is greater than at Mn.

Table II summarizes the properties of the lower molecular weight (LMW)component and the higher molecular weight (HMW) component of thepolymers of Examples 2-8. The respective LMW and HMW componentproperties were determined by deconvoluting the molecular weightdistribution (see FIGS. 1-8) of each polymer. The relative amounts ofthe LMW and HMW components (area percentages) in the polymer, and Mp ofthe LMW component and Mp of the HMW component, were determined using acommercial software program (Systat Software, Inc., Peak FitTM v. 4.05).The other molecular weight parameters for the LMW and HMW components(e.g., Mn, Mw, Mz, etc., of each component) were determined by using thedeconvoluted data from the Peak Fit™ program, and applying aSchulz-Flory distribution mathematical function and a Gaussian peak fit,as generally described in U.S. Pat. No. 7,300,983, which is incorporatedherein by reference in its entirety. The ratios of the Mp of the HMWcomponent to the Mp of the LMW component for the polymers of Examples2-8 were in the 7:1 to 15:1 range.

The LCB of the polymers of Examples 2-9 were determined usingJanzen-Colby method, as described herein. The LCB of the HMW componentwas determined by first producing a polymer using Metallocene B alone atconditions suitable to produce a polymer having a molecular weight (Mw)in the 100-125 kg/mol range, and then determining the LCB content usingthe Janzen-Colby method. The LCB of the LMW component was likewisedetermined by first producing a polymer using Metallocene A alone atconditions suitable to produce a polymer having a Mw in the 100-125kg/mol range, and then determining the LCB content using theJanzen-Colby method. The polymerization runs used to produce thesepolymers were conducted in a one-gallon stainless steel reactor with 1.8L of isobutane. About 1 mmol triisobutylaluminum, 100 mg of fluoridedsilica-coated alumina, and 3 mg of the respective metallocene compoundwere added in that order through a charge port while slowly ventingisobutane vapor. The charge port was closed and isobutane was added. Thecontents of the reactor were stirred and heated to the polymerizationtemperature of 80° C., and ethylene and 40 mL of 1-hexene were thenintroduced into the reactor. Ethylene was fed on demand to maintain thetarget pressure of 400 psig pressure for the 30 min length of thepolymerization run. If needed, hydrogen was added with the ethylene feedto produce a polymer with a Mw in the 100-125 kg/mol range. The reactorwas maintained at the desired temperature throughout the run by anautomated heating-cooling system. Using Metallocene A, polymers wereproduced at a Mw of 110 kg/mol and at a Mw of 112 kg/mol, and thesepolymers had 12.4 and 12.3 LCB, respectively, per million carbon atoms.Using Metallocene B, polymers were produced at a Mw of 107 kg/mol and at122 kg/mol, and both polymers had 1.1 LCB per million carbon atoms.Hence, the ratio of the number of LCB of the LMW component to the numberof LCB of the HMW component, per million total carbon atoms, was about11:1.

Blown films were produced under the HDPE conditions provided hereinaboveat an output rate of 28-30 lb/hr and a melt temperature of 191-192° C.In Table III, blown films labeled with an “A” were made without apolymer processing aid (e.g., Example 3A), while those labeled with a“B” were made with 400-800 ppm of a polymer processing aid (e.g.,Example 3B). Gels were measured using an automated camera-based gelcounting machine made by Optical Control System (OCS), Model FS-5. Thesystem consisted of a light source and a detector. The film was passedthrough the system, between the light source and the detector, with a150 mm (6 inch) inspection width. A total of 10 square meters of filmarea was inspected and the gels with sizes less than or greater than 200microns were analyzed. The numbers in the table represent the numbers ofeach category of gel sizes counted per square foot. Films made from thepolymers of Examples 2-6, as shown in Table III, exhibited a uniquecombination of dart impact strength, MD tear strength, haze, COF, andshrink properties. In particular, the films made from the polymers ofExamples 2-6 had dart impact strengths 3-7 times greater than that ofthe film produced from the polymer of Example 1, as well as a betterbalance of MD tear strength and TD tear strength.

Blown films were produced under the LLDPE conditions providedhereinabove at an output rate of about 27 kg/hr (60 lb/hr) and a melttemperature of 179-184° C., except for Example 2, which was produced atan output rate of 45-48 lb/hr due to pressure limitations. In TablesIV-V, blown films with an “A” were made without a polymer processing aid(e.g., Example 3A), while those with a “B” were made with 400-800 ppm ofa polymer processing aid (e.g., Example 3B). Films made from thepolymers of Examples 2-8, as shown in Table IV, exhibited a uniquecombination of dart impact strength, MD tear strength, haze, COF, andshrink properties. In particular, the films made from the polymers ofExamples 2-8 had lower gels and higher dart impact strengths than thatof the film produced from the polymer of Example 1, as well as a betterbalance of MD tear strength and TD tear strength.

TABLE I Polymer Properties of Examples 1-9. 1 2 3 4 5 6 7 8 9 Melt Index0.16 0.04 0.08 0.14 0.18 0.07 0.31 0.57 1.01 HLMI 15.9 5.1 12.7 9.6 15.76.7 24.0 59.6 92.9 HLMI/MI 99 128 159 69 87 95 77 105 92 Density 0.92460.9223 0.9242 0.9189 0.9220 0.9219 0.9249 0.9243 0.9252 Molecular weightparameters (kg/mol) Mn 11.6 16.6 16.1 17.5 15.7 17.3 14.1 14.4 14.7 Mw181 214 189 181 167 192 149 138 123 Mz 896 759 764 644 657 72 727 729673 Mw/Mn 15.6 12.9 11.7 10.3 10.7 11.1 10.6 9.6 8.4 Mz/Mw 5.0 3.5 4.13.6 3.9 3.8 4.9 5.3 5.5 Mp 77.5 26.2 28.0 120.4 55.1 55.1 36.6 37.6 36.6Dynamic Rheology @ 190° C. η₀ (Pa-sec) 6.3E+05 1.5E+05 1.0E+05 7.4E+048.2E+04 1.7E+05 6.3E+04 4.3E+04 3.4E+04 Tau(η) (sec) 2.30 1.33 1.11 0.410.52 1.18 0.54 0.27 0.12 CY-a 0.176 0.415 0.385 0.330 0.290 0.300 0.2500.228 0.193 LCB content (per 1,000,000 carbon atoms) and SCBdistribution (SCBD) LCB content 12.7 3.7 3.6 3.3 4.5 4.6 7.4 7.4 10.1SCBD reverse reverse reverse reverse reverse reverse reverse reversereverse

TABLE II Lower Molecular Weight and Higher Molecular Weight ComponentProperties of Examples 2-8. Lower Molecular Component Properties(kg/mol) Higher Molecular Weight Component Properties (kg/mol) Mp(HMW)/% Mn Mw Mz Mp Mw/Mn Mz/Mw % Mn Mw Mz Mp Mw/Mn Mz/Mw Mp(LMW) 2 54 10.538.4 113.7 20.1 3.7 3.0 46 164.4 406.1 736.7 258.4 2.5 1.8 13 3 62 10.839.8 111.5 20.8 3.7 2.8 38 178.0 424.8 762.9 275.0 2.4 1.8 13 4 45 11.045.2 185.9 22.3 4.1 4.1 55 99.6 438.7 746.4 186.4 4.4 1.7 8 5 58 11.446.6 115.0 23.0 4.1 2.5 42 120.8 362.5 715.4 209.3 3.0 2.0 9 6 56 9.452.3 213.0 22.1 5.6 4.1 44 116.9 367.7 780.6 267.3 3.1 2.1 12 7 72 12.847.6 133.1 24.7 3.7 2.8 28 123.7 417.8 831.5 227.3 3.4 2.0 9 8 75 15.358.3 134.2 29.9 3.8 2.3 25 151.1 453.2 812.1 261.6 3.0 1.8 9

TABLE III Film Properties of Examples 1-6 at 1 mil - HDPE processingconditions. HDPE 1 2A 2B 3A 3B 4A 4B 5B 6A 6B Gels <200 μm 289 82 120 9380 121 197 433 83 119 Gels >200 μm 49 49 141 40 42 46 75 121 32 54 DartImpact (g) 173 1003 936 965 741 1274 1128 861 634 978 MD Tear (g) 41 11184 108 85 121 91 107 99 82 TD Tear (g) 473 206 232 310 257 333 296 288243 249 Haze, % 43.5 86.0 85.8 83.3 84.7 68.2 66.9 69.4 78.7 80.4Spencer 0.51 1.94 1.91 1.88 1.85 1.86 1.85 1.82 1.86 1.87 Impact (J)Kinetic COF 0.315 0.350 0.331 0.345 0.341 0.379 0.410 0.381 0.364 0378(in/in) Static COF 0.334 0.401 0.378 0.438 0.416 0.480 0.464 0.441 0.4010.440 (in/in) Oil Shrinkage at 250 F. MD (%) 35 53 53 45 57 52 42 43 4035 TD (%) 27 45 42 40 40 42 28 33 27 23 Oil Shrinkage at 275 F. MD (%)73 65 67 68 65 58 58 67 65 62 TD (%) 43 55 48 48 45 43 40 52 47 47 OilShrinkage at 300 F. MD (%) 80 72 75 70 70 70 70 75 70 70 TD (%) 43 52 5050 50 48 45 45 52 47

TABLE IV Film Properties of Examples 1-8 at 1 mil - LLDPE processingconditions. LLDPE 1 2A 2B 3A 3B 4A 4B 5B 6A 6B 7B 8A Gels <200 μm 87 843 3 3 35 2 63 6 2 33 21 Gels >200 μm 43 55 2 1 2 11 2 27 2 1 17 6 DartImpact (g) 53 513 984 378 603 1285 1376 685 1305 1225 120 109 MD Tear(g) 35 23 67 40 75 63 97 74 89 62 82 112 TD Tear (g) 817 678 752 855 874543 634 688 518 674 466 419 Haze, % 42.1 91.3 94.1 91.9 91.0 75.6 68.975.3 85.7 86.1 85.9 77.9 Spencer 1.12 1.90 1.93 1.88 1.92 1.90 1.91 1.901.92 1.93 0.39 0.39 Impact (J) Kinetic COF 0.328 0.338 0.340 0.336 0.3430.398 0.372 0.373 0.347 0.353 0.346 0.372 (in/in) Static COF 0.352 0.4080.393 0.406 0.427 0.425 0.453 0.451 0.393 0.404 0.391 0.448 (in/in) OilShrinkage at 250 F. MD (%) 20 33 33 42 38 57 48 38 35 27 25 30 TD (%) 815 13 13 17 13 12 12 15 13 12 13 Oil Shrinkage at 275 F. MD (%) 80 80 7072 75 77 77 73 70 75 75 70 TD (%) 13 3 13 25 13 10 20 8 28 13 13 13 OilShrinkage at 300 F. MD (%) 84 80 80 77 80 80 80 80 75 80 80 80 TD (%) 1015 20 13 15 15 20 15 30 15 20 15

TABLE V Film Properties of Examples 1-8 at 3 mils - LLDPE processingconditions. LLDPE 1 2A 2B 3A 3B 4A 4B 5B 6A 6B 7B 8A Dart253 >1400 >1400 >1400 >1400 >1400 >1400 >1400 >1400 >1400 107 353 Impact(g) MD 255 284 415 433 514 520 516 565 487 384 433 652 Tear (g) TD 17921201 1260 1346 1293 1127 1100 1282 1165 1100 900 1201 Tear (g) Haze,47.6 95.4 95.4 91.2 89.8 79.2 72.9 71.2 88.7 88.2 82.4 76.1 % Spencer1.29 2.18 2.20 2.20 2.19 2.17 2.15 2.18 2.18 2.16 0.84 0.88 Impact (J)Kinetic 0.317 0.327 0.335 0.327 0.327 0.365 0.373 0.354 0.332 0.3490.335 0.347 COF (in/in) Static 0.323 0.396 0.464 0.457 0.448 0.466 0.4960.463 0.425 0.425 0.407 0.479 COF (in/in) Oil Shrinkage at 250 F. MD (%)10 40 25 13 20 15 12 18 18 28 40 20 TD (%) 5 13 12 3 3 5 10 13 8 15 8 8Oil Shrinkage at 275 F. MD (%) 52 53 55 63 62 58 65 60 55 60 65 53 TD(%) 15 13 10 15 20 15 15 15 18 13 12 15 Oil Shrinkage at 300 F. MD (%)75 70 65 65 65 65 70 70 70 70 70 57 TD (%) 15 25 25 15 25 15 20 20 20 1715 20

The invention is described above with reference to numerous aspects andembodiments, and specific examples. Many variations will suggestthemselves to those skilled in the art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims. Other embodiments of the invention caninclude, but are not limited to, the following (embodiments aredescribed as “comprising” but, alternatively, can “consist essentiallyof” or “consist of”):

Embodiment 1. An olefin polymer comprising a higher molecular weightcomponent and a lower molecular weight component, wherein the olefinpolymer has:

a ratio of the Mp of the higher molecular weight component to the Mp ofthe lower molecular weight component in a range from about 5:1 to about100:1;

a number of LCB of the lower molecular weight component in a range fromabout 5 to about 50 LCB per million total carbon atoms; and

a number of LCB of the higher molecular weight component of less than orequal to about 5 LCB per million total carbon atoms.

Embodiment 2. An olefin polymer comprising a higher molecular weightcomponent and a lower molecular weight component, wherein:

the lower molecular weight component has a Mp in a range from about 15to about 80 kg/mol, and from about 5 to about 50 LCB per million totalcarbon atoms; and

the higher molecular weight component has a Mp in a range from about 150to about 800 kg/mol, and less than or equal to about 5 LCB per milliontotal carbon atoms.

Embodiment 3. An olefin polymer comprising a higher molecular weightcomponent and a lower molecular weight component, wherein the olefinpolymer has:

a ratio of the Mp of the higher molecular weight component to the Mp ofthe lower molecular weight component in a range from about 5:1 to about100:1; and

a ratio of the number of LCB of the olefin polymer to the number of LCBof the higher molecular weight component, per millions total carbonatoms, in a range from about 2:1 to about 100:1.

Embodiment 4. An olefin polymer comprising a higher molecular weightcomponent and a lower molecular weight component, wherein the olefinpolymer has:

a ratio of the Mp of the higher molecular weight component to the Mp ofthe lower molecular weight component in a range from about 5:1 to about100:1;

a number of LCB of the higher molecular weight component of less than orequal to about 5 LCB per million total carbon atoms; and

a number of LCB of the olefin polymer in a range from about 2 to about30 LCB per million total carbon atoms.

Embodiment 5. The olefin polymer defined in any one of embodiments 1-4,wherein an amount of the higher molecular weight component, based on thetotal polymer, is in any range of area percentages disclosed herein,e.g., from about 10 to about 60%, from about 15 to about 50%, from about20 to about 55%, from about 20 to about 45%, from about 20 to about 40%,etc.

Embodiment 6. The olefin polymer defined in any one of embodiments 1-5,wherein a ratio of the Mp of the higher molecular weight component tothe Mp of the lower molecular weight component is any range disclosedherein, e.g., from about 2:1 to about 100:1, from about 5:1 to about100:1, from about 5:1 to about 30:1, from about 7:1 to about 50:1, fromabout 8:1 to about 25:1, etc.

Embodiment 7. The olefin polymer defined in any one of embodiments 1-6,wherein the lower molecular weight component has a Mp in any rangedisclosed herein, e.g., from about 10 to about 100, from about 15 toabout 80, from about 20 to about 70, from about 30 to about 60, fromabout 18 to about 50, from about 18 to about 35 kg/mol, etc.

Embodiment 8. The olefin polymer defined in any one of embodiments 1-7,wherein the higher molecular weight component has a Mp in any rangedisclosed herein, e.g., from about 200 to about 1,000, from about 150 toabout 800, from about 200 to about 700, from about 150 to about 500,from about 250 to about 500, from about 175 to about 300 kg/mol, etc.

Embodiment 9. The olefin polymer defined in any one of embodiments 1-8,wherein a ratio of the number of LCB of the olefin polymer to the numberof LCB of the higher molecular weight component, per million totalcarbon atoms, is any range disclosed herein, e.g., from about 2:1 toabout 100:1, from about 3:1 to about 50:1, from about 2:1 to about 25:1,from about 2:1 to about 10:1, from about 3:1 to about 15:1, from about5:1 to about 10:1, from about 7:1 to about 10:1, etc.

Embodiment 10. The olefin polymer defined in any one of embodiments 1-9,wherein a number of LCB of the lower molecular weight component is inany range disclosed herein, e.g., from about 5 to about 100, from about5 to about 50, from about 8 to about 30, from about 5 to about 15, fromabout 5 to about 10 LCB per million total carbon atoms, etc.

Embodiment 11. The olefin polymer defined in any one of embodiments1-10, wherein a number of LCB of the higher molecular weight componentis any range disclosed herein, less than or equal to about 10 LCB, lessthan or equal to about 5 LCB, less than or equal to about 3 LCB, lessthan or equal to about 2 LCB, less than or equal to about 1 LCB permillion total carbon atoms, etc.

Embodiment 12. The olefin polymer defined in any one of embodiments1-11, wherein a number of LCB of the olefin polymer is in any rangedisclosed herein, e.g., from about 1 to about 50, from about 1 to about30, from about 2 to about 20, from about 1 to about 10, from about 3 toabout 12 LCB per million total carbon atoms, etc.

Embodiment 13. The olefin polymer defined in any one of embodiments1-12, wherein the olefin polymer has a density in any range disclosedherein, e.g., from about 0.91 to about 0.94, from about 0.915 to about0.935, from about 0.913 to about 0.93, from about 0.917 to about 0.928,from about 0.92 to about 0.928 g/cm³, etc.

Embodiment 14. The olefin polymer defined in any one of embodiments1-13, wherein the olefin polymer has a melt index in any range disclosedherein, e.g., less than or equal to about 1, less than or equal to about0.4, less than or equal to about 0.3, less than or equal to about 0.25,less than or equal to about 0.2 g/10 min, etc.

Embodiment 15. The olefin polymer defined in any one of embodiments1-14, wherein the olefin polymer has a HLMI in any range disclosedherein, e.g., from about 3 to about 60, from about 4 to about 30, fromabout 4 to about 25, from about 4 to about 20, from about 5 to about 18,from about 5 to about 15 g/10 min, etc.

Embodiment 16. The olefin polymer defined in any one of embodiments1-15, wherein the olefin polymer has a ratio of HLMI/MI in any rangedisclosed herein, e.g., from about 50 to about 300, from about 100 toabout 350, from about 150 to about 300, from about 180 to about 350,from about 60 to about 250, from about 60 to about 200, from about 70 toabout 225, etc.

Embodiment 17. The olefin polymer defined in any one of embodiments1-16, wherein the olefin polymer has a ratio of Mw/Mn in any rangedisclosed herein, e.g., from about 6 to about 50, from about 8 to about35, from about 10 to about 35, from about 12 to about 50, from about 14to about 35, from about 6 to about 20, from about 8 to about 16, etc.

Embodiment 18. The olefin polymer defined in any one of embodiments1-17, wherein the olefin polymer has a ratio of Mz/Mw in any rangedisclosed herein, e.g., from about 3 to about 12, from about 3 to about6, from about 3.5 to about 9, from about 3.5 to about 6, etc.

Embodiment 19. The olefin polymer defined in any one of embodiments1-18, wherein the olefin polymer has a Mw in any range disclosed herein,e.g., from about 100 to about 600, from about 175 to about 600, fromabout 120 to about 500, from about 190 to about 500, from about 120 toabout 300, from about 150 to about 350 kg/mol, etc.

Embodiment 20. The olefin polymer defined in any one of embodiments1-19, wherein the olefin polymer has a Mn in any range disclosed herein,e.g., from about 8 to about 60, from about 10 to about 50, from about 10to about 25, from about 12 to about 45 kg/mol, etc.

Embodiment 21. The olefin polymer defined in any one of embodiments1-20, wherein the olefin polymer has a CY-a parameter in any rangedisclosed herein, e.g., from about 0.2 to about 0.45, from about 0.25 toabout 0.4, from about 0.25 to about 0.38, from about 0.25 to about 0.35,etc.

Embodiment 22. The olefin polymer defined in any one of embodiments1-21, wherein the olefin polymer has a zero-shear viscosity in any rangedisclosed herein, e.g., from about 10,000 to about 500,000, from about60,000 to about 500,000, from about 20,000 to about 400,000, from about70,000 to about 400,000, from about 30,000 to about 300,000 Pa-sec, etc.

Embodiment 23. The polymer defined in any one of embodiments 1-22,wherein the olefin polymer has a Tau(_(i)) in any range disclosedherein, e.g., from about 0.1 to about 3, from about 0.6 to about 3, fromabout 1 to about 3, from about 0.2 to about 2, from about 0.4 to about 2sec, etc.

Embodiment 24. The olefin polymer defined in any one of embodiments1-23, wherein the olefin polymer has a reverse comonomer distribution,e.g., the number of SCB per 1000 total carbon atoms of the polymer at Mwis greater than at Mn, and/or the number of SCB per 1000 total carbonatoms of the polymer at Mz is greater than at Mw, and/or the number ofSCB per 1000 total carbon atoms of the polymer at Mz is greater than atMn.

Embodiment 25. The olefin polymer defined in any one of embodiments1-24, wherein a ratio of the number of SCB per 1000 total carbon atomsof the polymer at Mz to the number of SCB per 1000 total carbon atoms ofthe polymer at Mn is in any range disclosed herein, e.g., from about 1.1to about 5, from about 1.2 to about 4, from about 1.2 to about 2.5, etc.

Embodiment 26. The olefin polymer defined in any one of embodiments1-25, wherein the olefin polymer is an ethylene/α-olefin copolymer.

Embodiment 27. The olefin polymer defined in any one of embodiments1-26, wherein the olefin polymer is an ethylene/1-butene copolymer, anethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.

Embodiment 28. The olefin polymer defined in any one of embodiments1-27, wherein the olefin polymer is an ethylene/1-hexene copolymer.

Embodiment 29. An article comprising the olefin polymer defined in anyone of embodiments 1-28.

Embodiment 30. An article comprising the olefin polymer defined in anyone of embodiments 1-28, wherein the article is an agricultural film, anautomobile part, a bottle, a drum, a fiber or fabric, a food packagingfilm or container, a food service article, a fuel tank, a geomembrane, ahousehold container, a liner, a molded product, a medical device ormaterial, a pipe, a sheet or tape, or a toy.

Embodiment 31. A film comprising the olefin polymer defined in any oneof embodiments 1-28.

Embodiment 32. A blown film comprising an olefin polymer having a meltindex less than or equal to about 0.4 g/10 min, wherein the film has adart impact strength greater than or equal to about 300 g/mil.

Embodiment 33. The film defined in embodiment 32, wherein the film has adart impact strength in any range disclosed herein, e.g., in a rangefrom about 300 to about 2000, about 400 to about 2000, about 500 toabout 2000, about 600 to about 2000, about 700 to about 2000 g/mil, etc.

Embodiments 34. The film defined in embodiment 32 or 33, wherein thefilm has a haze (without additives) in any range disclosed herein, e.g.,greater than or equal to about 55, greater than or equal to about 65,greater than or equal to about 75, greater than or equal to about 80%,greater than or equal to about 85%, etc.

Embodiment 35. The film defined in any one of embodiments 32-34, whereinthe film has a MD shrink at 250° F. in any range disclosed herein, e.g.,in a range from about 20 to about 70, from about 35 to about 70, fromabout 25 to about 65, from about 27 to about 65%, from about 30 to about60%, etc.

Embodiment 36. The film defined in any one of embodiments 32-35, whereinthe film has a MD Elmendorf tear strength in any range disclosed herein,e.g., in a range from about 10 to about 150, from about 25 to about 150,from about 50 to about 150, from about 75 to about 150 g/mil, etc.

Embodiment 37. The film defined in any one of embodiments 32-36, whereinthe film has a kinetic COF (without additives) in any range disclosedherein, e.g., in a range from about 0.3 to about 0.5, from about 0.3 toabout 0.48, from about 0.32 to about 0.47, etc.

Embodiment 38. The film defined in any one of embodiments 32-37, whereinthe film comprises the olefin polymer defined in any one of embodiments1-28, e.g., the olefin polymer characterized by one or more of the MI(e.g., less than or equal to about 0.4, about 0.3, about 0.25, about 0.2g/10 min, etc.), HLMI (e.g., from about 3 to about 60, about 4 to about30, about 4 to about 25, about 4 to about 20, about 5 to about 18, about5 to about 15 g/10 min, etc.), density (e.g., from about 0.91 to about0.94, about 0.915 to about 0.935, about 0.913 to about 0.93, about 0.917to about 0.928, about 0.92 to about 0.928 g/cm³, etc.), Mw/Mn (e.g.,from about 6 to about 50, about 8 to about 35, about 10 to about 35,about 12 to about 50, about 14 to about 35, about 6 to about 20, about 8to about 16, etc.), etc., ranges disclosed herein.

Embodiment 39. A catalyst composition comprising catalyst component I,catalyst component II, an activator, and an optional co-catalyst,wherein catalyst component I produces a lower molecular weight componenthaving more long chain branches and less short chain branches than thehigher molecular weight component (e.g., a two carbon bridgedmetallocene compound containing two indenyl groups, an unbridgedzirconium based metallocene compound with two cyclopentadienyl groups,etc.), and catalyst component II produces a higher molecular weightcomponent having more short chain branches and less long chain branchesthan the lower molecular weight component (e.g., a single atom bridgedmetallocene compound containing a fluorenyl group).

Embodiment 40. The composition defined in embodiment 39, wherein thecatalyst composition contains only two metallocene compounds: one is atwo carbon bridged metallocene compound containing two cyclopentadienylgroups, two indenyl groups, or a cyclopentadienyl and an indenyl group;and the other is a single atom bridged metallocene compound containing afluorenyl group.

Embodiment 41. The composition defined in embodiment 39 or 40, whereinthe weight percentage of catalyst component I and catalyst component IIis in any range of weight percentages disclosed herein, e.g., the weightpercentage of catalyst component I is in a range from about 25 to about98%, from about 40 to about 95%, from about 55 to about 98%, from about60 to about 95%, etc., wherein the weight percentages are based on thetotal weight of catalyst components I and II.

Embodiment 42. The composition defined in any one of embodiments 39-41,wherein the activator comprises any activator disclosed herein.

Embodiment 43. The composition defined in any one of embodiments 39-42,wherein the activator comprises an aluminoxane compound, an organoboronor organoborate compound, an ionizing ionic compound, or any combinationthereof.

Embodiment 44. The composition defined in any one of embodiments 39-43,wherein the activator comprises an aluminoxane compound.

Embodiment 45. The composition defined in any one of embodiments 39-43,wherein the activator comprises an organoboron or organoborate compound.

Embodiment 46. The composition defined in any one of embodiments 39-43,wherein the activator comprises an ionizing ionic compound.

Embodiment 47. The composition defined in any one of embodiments 39-42,wherein the activator comprises an activator-support, theactivator-support comprising any solid oxide treated with anyelectron-withdrawing anion disclosed herein.

Embodiment 48. The composition defined in embodiment 47, wherein thesolid oxide comprises any solid oxide disclosed herein, e.g., silica,alumina, silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, zirconia, magnesia,boria, zinc oxide, etc., a mixed oxide thereof, or any mixture thereofand the electron-withdrawing anion comprises any electron-withdrawinganion disclosed herein, e.g., sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, etc., or any combination thereof.

Embodiment 49. The composition defined in embodiment 47, wherein theactivator-support comprises fluorided alumina, chlorided alumina,bromided alumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, or any combination thereof.

Embodiment 50. The composition defined in embodiment 47, wherein theactivator-support comprises fluorided alumina, sulfated alumina,fluorided silica-alumina, sulfated silica-alumina, fluoridedsilica-coated alumina, sulfated silica-coated alumina, or anycombination thereof.

Embodiment 51. The composition defined in embodiment 47, wherein theactivator-support comprises a fluorided solid oxide, a sulfated solidoxide, or any combination thereof.

Embodiment 52. The composition defined in embodiment 47, wherein theactivator-support further comprises any metal or metal ion disclosedherein, e.g., zinc, nickel, vanadium, titanium, silver, copper, gallium,tin, tungsten, molybdenum, zirconium, or any combination thereof.

Embodiment 53. The composition defined in any one of embodiments 39-52,wherein the catalyst composition comprises a co-catalyst, e.g., anyco-catalyst disclosed herein.

Embodiment 54. The composition defined in any one of embodiments 39-53,wherein the co-catalyst comprises an organoaluminum compound, anorganozinc compound, an organomagnesium compound, an organolithiumcompound, or any combination thereof.

Embodiment 55. The composition defined in any one of embodiments 39-54,wherein the co-catalyst comprises an organoaluminum compound.

Embodiment 56. The composition defined in embodiment 55, wherein theorganoaluminum compound comprises any organoaluminum compound disclosedherein, e.g., trimethylaluminum, triethylaluminum, triisobutylaluminum,etc., or combinations thereof.

Embodiment 57. The composition defined in any one of embodiments 39-42,wherein the catalyst composition comprises catalyst component I,catalyst component II, a solid oxide treated with anelectron-withdrawing anion, and an organoaluminum compound.

Embodiment 58. The composition defined in any one of embodiments 47-57,wherein the catalyst composition is substantially free of aluminoxanecompounds, organoboron or organoborate compounds, ionizing ioniccompounds, or combinations thereof.

Embodiment 59. The composition defined in any one of embodiments 47-57,wherein the co-catalyst comprises an aluminoxane compound, anorganoboron or organoborate compound, an ionizing ionic compound, anorganoaluminum compound, an organozinc compound, an organomagnesiumcompound, an organolithium compound, or any combination thereof.

Embodiment 60. The composition defined in any one of embodiments 39-59,wherein catalyst component I comprises any catalyst component Imetallocene compound disclosed herein, e.g., a two carbon bridged,zirconium based metallocene compound containing two cyclopentadienylgroups, two indenyl groups, or a cyclopentadienyl and an indenyl group;an unbridged zirconium based metallocene compound with twocyclopentadienyl groups; a single atom bridged (C or Si), zirconiumbased metallocene compound with two cyclopentadienyl groups (e.g., withan alkyl substituent, such as propyl); a single atom bridged (C or Si),zirconium based metallocene compound with two indenyl groups (e.g.,meso-bridged); a 3-5 carbon atom bridged, zirconium based metallocenecompound with two indenyl groups (e.g., rac-bridged), etc.

Embodiment 61. The composition defined in any one of embodiments 39-59,wherein catalyst component I comprises a two carbon bridged, zirconiumbased metallocene compound containing two indenyl groups. Embodiment 62.The composition defined in any one of embodiments 39-59, whereincatalyst component I comprises any two carbon bridged metallocenecompound disclosed herein, e.g., having formula (A):

wherein:

M¹ is Zr or Hf; Cp¹ and Cp² independently are a cyclopentadienyl orindenyl group; E¹ is a bridging group having the formula—CR^(1A)R^(1B)—CR^(2A)R^(2B)—, wherein R^(1A), R^(1B), R^(2A), andR^(2B) independently are H or a hydrocarbyl group having up to 10 carbonatoms (e.g., any C₁-C₁₀ hydrocarbyl group disclosed herein); and each Xindependently is a monoanionic ligand.

Embodiment 63. The composition defined in embodiment 62, wherein M¹ isZr.

Embodiment 64. The composition defined in any one of embodiments 62-63,wherein Cp¹ and Cp² independently are a substituted indenyl orcyclopentadienyl group with any number of substituents disclosed herein,e.g., one substituent, two substituents, etc.

Embodiment 65. The composition defined in embodiment 64, wherein eachsubstituent on Cp¹ and Cp² independently is any substituent disclosedherein, e.g., H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁to C₃₆ hydrocarbylsilyl group; H or a hydrocarbyl group having up to 18carbon atoms, etc.

Embodiment 66. The composition defined in embodiment 62 or 63, whereinCp¹ and Cp² contain no additional substituents, e.g., other than thebridging group.

Embodiment 67. The composition defined in embodiment 62 or 63, whereinCp¹ and Cp² are indenyl groups containing no additional substituents,e.g., other than the bridging group.

Embodiment 68. The composition defined in any one of embodiments 62-67,wherein E¹ is a bridging group having the formula —CH₂—CH₂—.

Embodiment 69. The composition defined in any one of embodiments 39-68,wherein catalyst component II comprises a single atom bridged, zirconiumor hafnium based metallocene compound containing a cyclopentadienyl anda fluorenyl group.

Embodiment 70. The composition defined in embodiment 69, wherein thesingle atom is a carbon or silicon atom.

Embodiment 71. The composition defined in any one of embodiments 69-70,wherein the bridging group contains an aryl substituent (e.g., phenyl).

Embodiment 72. The composition defined in any one of embodiments 69-71,wherein the bridging group contains an alkenyl substituent (e.g., aterminal alkenyl).

Embodiment 73. The composition defined in any one of embodiments 39-68,wherein catalyst component II comprises any single atom bridgedmetallocene compound with a fluorenyl group disclosed herein, e.g.,having formula (B):

wherein:

M² is Zr or Hf; Cp is a cyclopentadienyl group; E² is carbon or silicon;R^(A) and R^(B) independently are H or a C₁ to C₁₈ hydrocarbyl group;R^(X) and R^(Y) independently are H, a halide, a C₁ to C₃₆ hydrocarbylgroup, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group; and each Xindependently is a monoanionic ligand.

Embodiment 74. The composition defined in embodiment 73, wherein M² isZr.

Embodiment 75. The composition defined in embodiment 73 or 74, whereinCp is a substituted cyclopentadienyl group with any number ofsubstituents disclosed herein, e.g., one substituent, two substituents,etc., in addition to the bridging group.

Embodiment 76. The composition defined in embodiment 75, wherein eachsubstituent on Cp independently is any substituent disclosed herein,e.g., H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁to C₃₆ hydrocarbylsilyl group; H or a hydrocarbyl group having up to 18carbon atoms, etc.

Embodiment 77. The composition defined in embodiment 73 or 74, whereinCp contains no additional substituents, e.g., other than the bridginggroup.

Embodiment 78. The composition defined in any one of embodiments 73-77,wherein E² is carbon.

Embodiment 79. The composition defined in any one of embodiments 73-78,wherein R^(A) and R^(B) independently are a C₁ to C₈ alkyl group, a C₃to C₈ alkenyl group, or a phenyl group.

Embodiment 80. The composition defined in any one of embodiments 73-79,wherein at least one of R^(A) and R^(B) is a phenyl group.

Embodiment 81. The composition defined in any one of embodiments 73-80,wherein at least one of R^(A) and R^(B) is a C₃ to C₈ terminal alkenylgroup.

Embodiment 82. The composition defined in any one of embodiments 73-78,wherein R^(A) and R^(B) independently are a methyl group, an ethylgroup, a propyl group, a butyl group, a pentyl group, a hexyl group, aheptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a cyclohexylphenyl group, a naphthyl group, atolyl group, or a benzyl group.

Embodiment 83. The composition defined in any one of embodiments 73-82,wherein R^(X) and R^(Y) independently are H or any C₁ to C₁₂ hydrocarbylgroup disclosed herein.

Embodiment 84. The composition defined in any one of embodiments 73-82,wherein R^(X) and R^(Y) independently are H, a methyl group, an ethylgroup, a propyl group, a butyl group, a pentyl group, a hexyl group, aheptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a tolyl group, or a benzyl group.

Embodiment 85. The composition defined in any one of embodiments 73-82,wherein R^(X) and R^(Y) independently are H or a C₁ to C₆ linear orbranched alkyl group (e.g., tert-butyl).

Embodiment 86. The composition defined in any one of embodiments 62-68and 73-85, wherein each X independently is any monoanionic liganddisclosed herein.

Embodiment 87. The composition defined in any one of embodiments 62-68and 73-85, wherein each X independently is H, BH₄, a halide, a C₁ to C₃₆hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, a C₁ to C₃₆hydrocarbylaminyl group, a C₁ to C₃₆ hydrocarbylsilyl group, a C₁ to C₃₆hydrocarbylaminylsilyl group, OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ toC₃₆ hydrocarbyl group.

Embodiment 88. The composition defined in any one of embodiments 62-68and 73-85, wherein each X independently is any halide or C₁ to C₁₈hydrocarbyl group disclosed herein.

Embodiment 89. The composition defined in any one of embodiments 62-68and 73-85, wherein each X is Cl.

Embodiment 90. The composition defined in any one of embodiments 39-89,wherein the catalyst composition is produced by a process comprisingcontacting, in any order, catalyst component I, catalyst component II,and the activator.

Embodiment 91. The composition defined in any one of embodiments 39-89,wherein the catalyst composition is produced by a process comprisingcontacting, in any order, catalyst component I, catalyst component II,the activator, and the co-catalyst.

Embodiment 92. The composition defined in any one of embodiments 39-91,wherein a catalyst activity of the catalyst composition is in any rangedisclosed herein, e.g., in a range from about 150 to about 10,000, fromabout 500 to about 7,500, from about 1,000 to about 5,000 grams, etc.,of ethylene polymer per gram of activator-support per hour, under slurrypolymerization conditions, with a triisobutylaluminum co-catalyst, usingisobutane as a diluent, and with a polymerization temperature of 90° C.and a reactor pressure of 390 psig.

Embodiment 93. An olefin polymerization process, the process comprisingcontacting the catalyst composition defined in any one of embodiments39-92 with an olefin monomer and an optional olefin comonomer in apolymerization reactor system under polymerization conditions to producean olefin polymer.

Embodiment 94. The process defined in embodiment 93, wherein the olefinmonomer comprises any olefin monomer disclosed herein, e.g., any C₂-C₂₀olefin.

Embodiment 95. The process defined in embodiment 93 or 94, wherein theolefin monomer and the optional olefin comonomer independently comprisea C₂-C₂₀ alpha-olefin.

Embodiment 96. The process defined in any one of embodiments 93-95,wherein the olefin monomer comprises ethylene.

Embodiment 97. The process defined in any one of embodiments 93-96,wherein the catalyst composition is contacted with ethylene and anolefin comonomer comprising a C₃-C₁₀ alpha-olefin.

Embodiment 98. The process defined in any one of embodiments 93-97,wherein the catalyst composition is contacted with ethylene and anolefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixturethereof.

Embodiment 99. The process defined in any one of embodiments 93-95,wherein the olefin monomer comprises propylene.

Embodiment 100. The process defined in any one of embodiments 93-99,wherein the polymerization reactor system comprises a batch reactor, aslurry reactor, a gas-phase reactor, a solution reactor, a high pressurereactor, a tubular reactor, an autoclave reactor, or a combinationthereof.

Embodiment 101. The process defined in any one of embodiments 93-100,wherein the polymerization reactor system comprises a slurry reactor, agas-phase reactor, a solution reactor, or a combination thereof.

Embodiment 102. The process defined in any one of embodiments 93-101,wherein the polymerization reactor system comprises a loop slurryreactor.

Embodiment 103. The process defined in any one of embodiments 93-102,wherein the polymerization reactor system comprises a single reactor.

Embodiment 104. The process defined in any one of embodiments 93-102,wherein the polymerization reactor system comprises 2 reactors.

Embodiment 105. The process defined in any one of embodiments 93-102,wherein the polymerization reactor system comprises more than 2reactors.

Embodiment 106. The process defined in any one of embodiments 93-105,wherein the olefin polymer comprises any olefin polymer disclosedherein.

Embodiment 107. The process defined in any one of embodiments 93-98 and100-106, wherein the olefin polymer is an ethylene homopolymer, anethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or anethylene/1-octene copolymer.

Embodiment 108. The process defined in any one of embodiments 93-98 and100-107, wherein the olefin polymer is an ethylene/1-hexene copolymer.

Embodiment 109. The process defined in any one of embodiments 93-95 and99-106, wherein the olefin polymer is a polypropylene homopolymer or apropylene-based copolymer.

Embodiment 110. The process defined in any one of embodiments 93-109,wherein the polymerization conditions comprise a polymerization reactiontemperature in a range from about 60° C. to about 120° C. and a reactionpressure in a range from about 200 to about 1000 psig (about 1.4 toabout 6.9 MPa).

Embodiment 111. The process defined in any one of embodiments 93-110,wherein the polymerization conditions are substantially constant, e.g.,for a particular polymer grade.

Embodiment 112. The process defined in any one of embodiments 93-111,wherein no hydrogen is added to the polymerization reactor system.

Embodiment 113. The process defined in any one of embodiments 93-111,wherein hydrogen is added to the polymerization reactor system.

Embodiment 114. An olefin polymer produced by the olefin polymerizationprocess defined in any one of embodiments 93-113.

Embodiment 115. An olefin polymer defined in any one of embodiments 1-28produced by the olefin polymerization process of any one of embodiments93-113.

Embodiment 116. An article comprising the olefin polymer defined in anyone of embodiments 114-115.

Embodiment 117. A method or forming or preparing an article ofmanufacture comprising an olefin polymer, the method comprising (i)performing the olefin polymerization process defined in any one ofembodiments 93-113 to produce an olefin polymer (e.g., the olefinpolymer of any one of embodiments 1-28), and (ii) forming the article ofmanufacture comprising the olefin polymer, e.g., via any techniquedisclosed herein.

Embodiment 118. The article defined in any one of embodiments 116-117,wherein the article is an agricultural film, an automobile part, abottle, a drum, a fiber or fabric, a food packaging film or container, afood service article, a fuel tank, a geomembrane, a household container,a liner, a molded product, a medical device or material, a pipe, a sheetor tape, or a toy.

Embodiment 119. The article defined in any one of embodiments 116-117,wherein the article is a film (e.g., a blown film) defined in any one ofembodiments 32-38.

We claim:
 1. An ethylene polymer comprising a higher molecular weight component and a lower molecular weight component, wherein the polymer has: a ratio of the Mp of the higher molecular weight component to the Mp of the lower molecular weight component in a range from about 5:1 to about 100:1; a number of LCB of the lower molecular weight component in a range from about 5 to about 50 LCB per million total carbon atoms; and a number of LCB of the higher molecular weight component of less than or equal to about 5 LCB per million total carbon atoms.
 2. The polymer of claim 1, wherein: the lower molecular weight component has a Mp in a range from about 15 to about 80 kg/mol; the higher molecular weight component has a Mp in a range from about 150 to about 800 kg/mol; a ratio of the number of LCB of the ethylene polymer to the number of LCB of the higher molecular weight component, per millions total carbon atoms, in a range from about 2:1 to about 100:1; and a number of LCB of the ethylene polymer in a range from about 2 to about 30 LCB per million total carbon atoms.
 3. The polymer of claim 1, wherein the amount of the higher molecular weight component, based on the weight of the ethylene polymer, is in a range from about 10 to about 60 area %.
 4. The polymer of claim 1, wherein the polymer has: a melt index of less than or equal to about 0.4 g/10 min; a high load melt index in a range from about 4 to about 30 g/10 min; and a density in a range from about 0.915 to about 0.935 g/cm³.
 5. The polymer of claim 4, wherein the polymer has: a ratio of Mw/Mn in a range from about 8 to about 35; a ratio of Mz/Mw in a range from about 3 to about 6; a Mw in a range from about 120 to about 500 kg/mol; a Mn in a range from about 10 to about 50 kg/mol; or any combination thereof.
 6. The polymer of claim 1, wherein the polymer has: a zero-shear viscosity at 190° C. in a range from about 10,000 to about 500,000 Pa-sec; a CY-a parameter at 190° C. in a range from about 0.20 to about 0.45; and a Tau(η) parameter at 190° C. in a range from about 0.2 to about 2 sec.
 7. The polymer of claim 1, wherein the polymer is an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.
 8. The polymer of claim 7, wherein the polymer has a reverse comonomer distribution.
 9. An article comprising the polymer of claim
 8. 10. A film comprising the polymer of claim
 8. 11. A blown film comprising an ethylene polymer having a melt index less than or equal to about 0.4 g/10 min, wherein the film has a dart impact strength greater than or equal to about 300 g/mil.
 12. The film of claim 11, wherein the polymer comprises a higher molecular weight component and a lower molecular weight component, wherein: a ratio of the Mp of the higher molecular weight component to the Mp of the lower molecular weight component in a range from about 5:1 to about 100:1; the lower molecular weight component has a Mp in a range from about 15 to about 80 kg/mol; and the higher molecular weight component has a Mp in a range from about 150 to about 800 kg/mol.
 13. The film of claim 12, wherein the polymer comprises a higher molecular weight component and a lower molecular weight component, wherein: a number of LCB of the lower molecular weight component is in a range from about 5 to about 50 LCB per million total carbon atoms; a number of LCB of the higher molecular weight component is less than or equal to about 5 LCB per million total carbon atoms; a number of LCB of the ethylene polymer is in a range from about 2 to about 30 LCB per million total carbon atoms; and a ratio of the number of LCB of the ethylene polymer to the number of LCB of the higher molecular weight component, per millions total carbon atoms, is in a range from about 2:1 to about 100:1.
 14. The film of claim 11, wherein the polymer is an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer, and is characterized by: a melt index of less than or equal to about 0.4 g/10 min; a high load melt index in a range from about 4 to about 30 g/10 min; a density in a range from about 0.915 to about 0.935 g/cm³; and a ratio of Mw/Mn in a range from about 8 to about
 35. 15. The film of claim 14, wherein the film has: a dart impact strength in a range from about 400 to about 2000 g/mil; a haze of greater than or equal to about 55%; a MD shrink at 250° F. in a range from about 20 to about 70%; a MD Elmendorf tear strength in a range from about 10 to about 150 g/mil; and a kinetic COF in a range from about 0.3 to about 0.5.
 16. A catalyst composition comprising: catalyst component I comprising a two carbon bridged metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group; catalyst component II comprising a single atom bridged metallocene compound containing a fluorenyl group; an activator; and optionally, a co-catalyst; wherein a weight percentage of catalyst component I is in a range from about 25 to about 98%, based on the total weight of catalyst component I and catalyst component II.
 17. The composition of claim 16, wherein: catalyst component I comprises a metallocene compound having formula (A):

wherein: M¹ is Zr or Hf; Cp¹ and Cp¹ independently are a cyclopentadienyl or indenyl group; E¹ is a bridging group having the formula —CR^(1A)R^(1B)—CR^(2A)R^(2B), wherein R^(1A), R^(1B), R^(2A), and R^(2B) independently are H or a hydrocarbyl group having up to 10 carbon atoms (e.g., any C₁-C₁₀ hydrocarbyl group disclosed herein); and each X independently is a monoanionic ligand; and catalyst component II comprises a metallocene compound having formula (B):

wherein: M² is Zr or Hf; Cp is a cyclopentadienyl group; E² is carbon or silicon; R^(A) and R^(B) independently are H or a C₁ to C₁₈ hydrocarbyl group; R^(X) and R^(Y) independently are H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group; and each X independently is a monoanionic ligand.
 18. The composition of claim 17, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.
 19. An olefin polymerization process, the process comprising contacting the catalyst composition of claim 17 with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.
 20. The process of claim 19, wherein: the activator comprises an activator-support comprising a fluorided solid oxide and/or a sulfated solid oxide; the catalyst composition comprises an organoaluminum co-catalyst; the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof; and the polymerization reactor system comprises a slurry reactor, gas-phase reactor, solution reactor, or a combination thereof. 